Compositions containing polymeric, ionic compounds comprising imidazolium groups

ABSTRACT

The present invention relates to compositions containing polymeric, ionic compounds comprising imidazolium groups. In particular, it relates to the use of polymeric, ionic compounds comprising imidazolium groups in personal care compositions and/or in biocide compositions.

BACKGROUND OF THE INVENTION

The present invention relates to compositions containing polymeric,ionic compounds comprising imidazolium groups. In particular, it relatesto the use of polymeric, ionic compounds comprising imidazolium groupsin personal care compositions and/or in biocide compositions and inparticular in fungicide compositions.

DESCRIPTION OF THE RELATED ART

Cationic polymers are widely used in various technical fields. They areemployed e.g. as the active component of biocide compositions fordiversified applications. They are also widely used in personal care andhousehold products to perform a function in the final product, ranginge.g. from thickening to conditioning of a substrate. Depending on theapplication, the substrate treated with a composition of a cationicpolymer can be skin, hair, leather, a textile substrate, the surface ofan object, etc. Cationic polymers can be used in haircare products toprovide conditioning to the hair. In skincare products, the samepolymers can provide conditioning effects to the skin. When incorporatedinto detergent and fabric softening formulations, the same polymers canprovide conditioning, softening, and antistatic characteristics tofabrics. There is a continuing demand for cationic polymers having anoverall good application profile for diverse areas of use.

According to German biocide law and the EU Biocidal Products Directive“biocides” are active substances or mixtures containing one or moreactive substances, intended to destroy, deter, render harmless, preventthe action of, or otherwise exert a controlling effect on any harmfulorganism by chemical or biological means. “Harmful organism” meansorganisms, including pathogenic agents, which have an unwanted presenceor a detrimental effect on humans, their activities or the products theyuse or produce, or on animals, plants or the environment. According tothe classification of the EU Biocidal Products Directive theclassification of biocides, is broken down into 23 product types (i.e.application categories). They can be roughly categorised in thefollowing main groups: general biocidal products, disinfectants,preservatives, pest control, anti-fouling products.

It is known to employ cationic oligomers and polymers as activecomponents of biocide compositions. WO 2006/117382 A1 teaches the use ofa cationic polymer selected from polyethylene imines and polyvinylamines comprising 0.1 to 22 milliequivalent cationic groups per gram ofpolymer as active biocidal substances.

JP 04-202305 describes a resin having a polystyrene based main chain anda graft-chain attached to a benzene ring of the main chain comprisingimidazolinium groups. Those resins are useful inter alia asantimicrobial agent.

G. Garg et al. describe in J. Colloid Interface Sci. 344 (2010), 90-96anion effects on anti-microbial activity of poly[1-vinyl-3-(2-sulfoethylimidazolium betaine)]. The employed polymers have a comb structure witha polyalkylene main chain and zwitterionic side chains comprising acationic imidazolium group and an anionic sulfonate group.

GB 2271718 A describes polyquaternary ammonium compounds of the formula:

where R¹ is hydrogen, alkyl, or aryl, each of R² and R³ is hydrogen oralkyl of 1 to 4 carbon atoms, R⁴ is hydrogen or methyl, X is hydroxyl orhalogen, and n is an integer, that are useful as antimicrobial agents,especially against fungi and bacteria.

WO 98/49898 describes biocidal agents comprising quaternary cationicsurfactants having two imidazolinium groups.

WO 94/08972 describes inter alia the use of oligomeric imidazolium saltsas swimming pool sanitizers having improved compatibility with chlorine.The oligomeric imidazolium salts comprise at the most 7 repeat units andthe main chain is terminated by C₁-C₂₄-hydrocarbyl groups at both ends.The anion is especially halide, such as chloride, iodide and inparticular bromide.

WO 03/000221 describes a composition for the treatment of acne andfurther skin problems that are accompanied by a hyperseborrhoea. Thecomposition comprises at least one polymeric compound with quaternaryammonium groups in the main chain that are at least partly derived fromimidazolium groups. In the concrete embodiments the main chain comprisesin addition at least one 1,4-bound benzene ring and/or a quaternaryammonium ion derived from an acyclic amine.

WO 2010/072571 relates to a method for producing polymeric, ionicimidazolium compounds, characterized in that an α-dicarbonyl compound,an aldehyde, at least one amino compound having at least two primaryamino groups, optionally an amino compound having only one primary aminogroup, and a hydracid are reacted with each other. It is not disclosedto employ the obtained imidazolium compounds as biocides.

There is a continuing demand for biocides that simultaneously meet thecomplex application requirements of various different uses.

In the field of personal care compositions, cationic polymers are usedinter alia in detergent cosmetic compositions employed for cleansing andcaring the hair or the skin. Detergent compositions may additionallycomprise at least one cosmetically acceptable active ingredient that isbeneficial to keratin materials.

US 2009/0048132 A1 (EP 2 011 477) describes a detergent and conditioningcomposition comprising, in a cosmetically acceptable aqueous medium, atleast one cationic polymer, a mixture of 4 different surfactants and atleast one beneficial agent other than the cationic polymer. Thecomposition is used in particular for cleansing and caring the hair orthe skin.

US 2009/0074692 A1 teaches to use a combination of at least one cationicpolymer and at least one associative polymer in cosmetic conditioningcompositions.

FR 2920975 A1 describes a composition for antidandruff treatment of hairand scalp that comprises selenium disulfide and one or more cationicpolymers obtained by polymerization of a mixture of monomers comprisingone or more vinyl monomers substituted by amino groups, one or morehydrophobic non-ionic vinyl monomers and one or more associative vinylmonomers.

FR 2912908 A1 describes a hair dye composition comprising a cationic dyeand a cationic polymer.

US 2008/131391 A1 (EP 1 927 344) describes a composition for treating akeratinous substrate, comprising: a) at least one quaternary ammoniumpolymer, b) at least one fatty quaternary agent, c) at least onenonionic surfactant, and d) optionally, at least one ceramide.

FR 2910276 A1 describes a composition for treating a keratinoussubstrate, comprising a cationic polymer and alkoxysilanes withsolubilizing functional groups, to avoid any degradation in hair feel onrepeated application of the composition.

It has now been found, surprisingly, that polymeric, ionic compoundscomprising imidazolium groups of the type described in WO 2010/072571can be advantageously employed as biocides. Due to their uniqueapplication properties they are in particular suitable for a use in thistechnical field. It was also surprisingly found that irrespective oftheir biocidal activity those polymeric, ionic compounds comprisingimidazolium groups can be advantageously employed as an alternative ofknown cationic polymers. They have an overall good application profilefor diverse areas of use, e.g. in personal care compositions, home carecompositions, compositions used for material protection, pharmaceuticalcompositions, plant protection compositions, etc. In particular,advantageous properties are obtained if conventional cationic polymersused in personal care compositions are replaced completely or partly byat least one polymeric, ionic compound comprising imidazolium groups.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides a biocide composition,comprising at least one polymeric, ionic compound comprising imidazoliumgroups (imidazolium compound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal;where the main chain of the at least one compound comprising imidazoliumgroups does not contain 1,4-bound phenylene rings and specifically doesnot contain phenylene rings;where the amino compound having at least two primary amino groups is not1,3-diamino-2-hydroxy-propane or 1,3-diamino-2-hydroxy-2-methyl-propane;andwhere the polymer comprises at least 8, preferably at least 10imidazolium rings;and at least one carrier and/or at least one auxiliary agent.

Especially, the main chain of the at least one imidazolium compoundapart from the nitrogen atoms of the imidazolium groups does not containany quaternary nitrogen atoms that bear 4 residues that are differentfrom hydrogen.

Especially, the main chain of the at least one imidazolium compound doesnot contain quaternary ammonium groups of the formula —(N⁺R^(A)R^(B))—,wherein R^(A) and R^(B) may have the same or different meanings,selected from alkyl, monohydroxyalkyl and polyhydroxyalkyl.

In particular, the biocide composition according to the invention is:

-   -   a plant protection composition; especially a fungicidal        composition, or    -   a personal care composition, or    -   a home care composition, or    -   a composition used for industrial or institutional or hospital        disinfection,    -   a material protection composition, or    -   a pharmaceutical composition.

Special embodiments of the personal care composition according to theinvention are:

-   -   a cosmetic composition, or    -   a hygiene composition.

In a further aspect, the invention provides an antimicrobial polymercomposition or coating composition, wherein the polymer composition orthe coating comprises an effective antimicrobial amount of at least onepolymeric, ionic compound comprising imidazolium groups, as definedabove and in the following.

The imidazolium compounds according to the invention show a rapid effectand a broad range of applications against various microorganisms. Thus,in a first variant, the imidazolium compound can be used asdisinfectants and general biocidal products, e.g. as defined in maingroup 1 of the EU Biocidal Products Directive (Directive 98/8/EC). Theimidazolium compounds according to the invention can be usedadvantageously as or in:

-   -   Human hygiene biocidal products    -   Private area and public health area disinfectants and other        biocidal products    -   Veterinary hygiene biocidal products    -   Food and feed area disinfectants    -   Drinking water disinfectants

The imidazolium compounds according to the invention also show amicrobiostatic effect over a long period of time effect against variousmicroorganisms. Thus, in a second variant, the imidazolium compound canbe used as preservatives, e.g. as defined in main group 2 of the EUBiocidal Products Directive (Directive 98/8/EC). The imidazoliumcompounds according to the invention can be used advantageously as orin:

-   -   In-can preservatives    -   Film preservatives    -   Wood preservatives    -   Fibre, leather, rubber and polymerised materials preservatives    -   Masonry preservatives    -   Preservatives for liquid-cooling and processing systems    -   Slimicides    -   Metalworking-fluid preservatives

In a further aspect, the invention provides a method for combatingharmful organisms or for protecting human beings, animals, materials orprocesses from the effects of these harmful organisms, wherein thehabitat of the harmful organism or the human being, animal or materialto be protected is brought into contact with a biocide composition orthe biocide composition is employed in said process, wherein the biocidecomposition comprises at least one polymeric, ionic compound comprisingimidazolium groups, as defined above and in the following.

In a further aspect, the invention provides a method for combatingharmful fungi, which method comprises treating the fungi or materials,plants, parts thereof, the locus where the plants grow or are to grow orplants' propagation material to be protected from fungal attack with aneffective amount of at least one polymeric, ionic compound comprisingimidazolium groups (imidazolium compound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal;or with a composition comprising said polymeric, ionic compound.

Preferably, the amino compound c) having at least two primary aminogroups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane.

Alternatively or additionally, the polymer comprises preferably at least8, more preferably at least 10 imidazolium rings

More preferably, the ionic compound comprising imidazolium groups is asdefined above and in the following.

In a further aspect, the invention provides the use of at least oneimidazolium compound, as defined above and in the following, as biocide.

In a further aspect, the invention provides the use of of at least onepolymeric, ionic compound comprising imidazolium groups (imidazoliumcompound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal;for combating harmful fungi.

Preferably, the amino compound c) having at least two primary aminogroups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane.

Alternatively or additionally, the polymer comprises preferably at least8, more preferably at least 10 imidazolium rings

More preferably, the ionic compound comprising imidazolium groups is asdefined above and in the following.

In a further aspect, the invention provides a composition, comprising atleast one imidazolium compound, as defined above and in the following,wherein the imidazolium compound performs a function in the finalproduct different from the function as biocide. The imidazolium compoundmay perform this function as an alternative to or in addition to thefunction as biocide.

A preferred embodiment of a composition, wherein the imidazoliumcompound performs a function in the final product different from thefunction as biocide, is a personal care composition, comprising

-   A) at least one polymeric, ionic compound comprising imidazolium    groups (imidazolium compound), obtainable by reacting    -   a) at least one α-dicarbonyl compound,    -   b) at least one aldehyde,    -   c) at least one amino compound having at least two primary amino        groups,    -   d) optionally an amino compound having only one primary amino        group and    -   e) at least one protic acid,    -   and optionally subjecting the reaction product to an anion        exchange,    -   where the main chain of the at least one compound comprising        imidazolium groups does not contain benzene rings, and    -   where in the components a) and b) the aldehyde carbonyl groups        may also be present as hemiacetal or acetal and the ketone        carbonyl groups may also be present as hemiketal or ketal,-   C) optionally at least one cosmetically acceptable active    ingredient, and-   D) optionally at least one cosmetically acceptable auxiliary.

A first special embodiment is a cosmetic composition, comprising in acosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following,    -   at least one surfactant and    -   at least one cosmetically acceptable active ingredient that is        beneficial to keratin materials.

The combination of at least one imidazolium compound according to theinvention, at least one surfactant and at least one cosmeticallyacceptable active ingredient that is beneficial to keratin materials maylead to an increase of the deposition of the beneficial agent on keratinmaterials and thereby to an increase in the efficacy of said beneficialagents or to reduce the amount of said agent used.

A second special embodiment is a cosmetic composition, comprising in acosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one associative polymer.

Cosmetic compositions, in particular hair compositions, such as ashampoo or a conditioner, are most commonly in the form of a liquidhaving different viscosities. Products of which the texture issufficiently thick to remain on the hair, without running, for a certainperiod of time, are desirable. This thickener, or even gel, texture,should not impair the qualities of the product when used. The use ofconventional thickener polymers having usually very high molar massescreates problems, such as a relatively unpleasant texture and poorspreadability of the gels obtained. It was now surprisingly found that acosmetic composition comprising at least one imidazolium compoundaccording to the invention and at least one associative polymer remediesthese drawbacks. The compositions according to the present inventiongive hair more mass, more body, and more sheen compared withcompositions comprising an associative polymer in the absence of atleast one imidazolium compound.

A third special embodiment is an antidandruff composition, comprising ina cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   optionally at least one antidandruff agent different from the        imidazolium compound.

Antidandruff products, which have been proposed in order to combat theformation of dandruff, which is generally accompanied by a microbialand/or fungal proliferation, are either products which inhibit microbialproliferation, or keratolytic products. However, hair treated withantidandruff agents has a coarse, charged feel. In addition, the use ofcationic polymers from the prior art for this purpose can presentvarious drawbacks. On account of their high affinity for the hair, someof these polymers can become deposited in large amount during repeateduse, and give undesirable effects, such as an unpleasant, charged feel,stiffness of the hair and an inter-fibre adhesion which affects styling.It has now been surprisingly found that the imidazolium compounds of theinvention used alone or in combination with conventional antidandruffagents can allow these drawbacks to be overcome or lessened.

A fourth special embodiment is a composition for the treatment of acneand cutaneous disorders linked to hyperseborrhoea, comprising in acosmetically acceptable medium at least one imidazolium compound(=component A), as defined above and in the following.

A fifth special embodiment is a hair dye composition, comprising in acosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one dye, preferably at least one cationic dye.

A sixth special embodiment is a cosmetic composition for treating akeratinous substrate, comprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one fatty quaternary amine.

A seventh special embodiment is a cosmetic composition for treating akeratinous substrate, comprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one alkoxysilane with solubilizing functional groups.

In a further aspect, the invention provides the use of at least oneimidazolium compound, as defined above and in the following, asauxiliary in pharmacy, preferably as or in (a) coating(s) for solid drugforms, as surface-active compound, as or in (an) adhesive(s) and as orin (a) coating(s) for the textile, paper, printing and leather industry.

DESCRIPTION OF THE INVENTION

In the context of the invention, the expression “harmful organism”comprises organisms which have a detrimental effect on humans, theiractivities or the products they use or produce, or on animals or theenvironment. This includes pathogenic agents. The term “harmfulorganism” also comprises organisms which have an unwanted presence.

In the context of the invention, the expression “unsubstituted orsubstituted alkyl, alkoxy, alkylthio, cycloalkyl, cycloalkoxy,cycloalkylthio, aryl, aryloxy, arylthio”, represents unsubstituted orsubstituted alkyl, unsubstituted or substituted alkoxy, unsubstituted orsubstituted alkylthio, unsubstituted or substituted cycloalkyl,unsubstituted or substituted cycloalkoxy, unsubstituted or substitutedcycloalkylthio, unsubstituted or substituted aryl, unsubstituted orsubstituted aryloxy, unsubstituted or substituted arylthio.

In the context of the present invention, the expression “alkyl”comprises straight-chain or branched alkyl groups. Alkyl is preferablyC₁-C₃₀-alkyl, more preferably C₁-C₂₀-alkyl even more preferablyC₁-C₁₂-alkyl and in particular C₁-C₆-alkyl. Examples of alkyl groups areespecially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-hexadecyl, n-octadecyl and n-eicosyl.

Examples for C₁-C₆-alkyl are methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl,and position isomers thereof.

Examples for C₁-C₁₂-alkyl are, apart those mentioned above forC₁-C₆-alkyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl,2-propylheptyl, n-undecyl, n-dodecyl and position isomers thereof.

Examples for C₁-C₂₀-alkyl are, apart those mentioned above forC₁-C₁₂-alkyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl, n-eicosyl and position isomers thereof.

Examples for C₁-C₃₀-alkyl are, apart those mentioned above forC₁-C₂₀,-alkyl, n-henicosyl, n-docosy, n-tricosyl, n-tetracosy,n-pentacosyl, n-hexacosyl, n-octacosy, n-nonacosyl, n-triacontyl andposition isomers thereof.

The expression alkyl also comprises alkyl radicals whose carbon chainsmay be interrupted by one or more nonadjacent groups which are selectedfrom —O—, —S—, —NR^(b)—, —C(═O)—, —S(═O)— and/or —S(═O)₂—. R^(b) ispreferably hydrogen, alkyl, cycloalkyl aryl or a groupCH₂CH₂—O_(y)—R^(c), wherein y is 1, 2, 3, 4, 5 or 6 and R^(c) ishydrogen or C₁-C₄-alkyl. Preferably however, the term alkyl does notcomprise alkyl radicals whose carbon chains may be interrupted by one ormore nonadjacent groups which are selected from —O—, —S—, —NR^(b)—,—C(═O)—, —S(═O)— and/or —S(═O)₂— unless explicitly specified.

Substituted alkyl groups may, depending on the length of the alkylchain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5)substituents. These are preferably each independently selected fromcycloalkyl, aryl, fluorine, chlorine, bromine, hydroxyl, mercapto,cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate,alkylcarbonyloxy, carbamoyl, SO₃H, sulfonate, sulfamino, sulfamide,amidino, NE¹E², where E¹ and E² are each independently hydrogen, alkyl,cycloalkyl or aryl. Cycloalkyl and aryl substituents of the alkyl groupsmay in turn be unsubstituted or substituted; suitable substituents arethe substituents mentioned below for these groups.

The above remarks regarding alkyl also apply to the alkyl moiety inalkoxy (an alkyl radical bound via an oxygen atom to the remainder ofthe molecule) and alkylthio (=alkylsulfanyl; an alkyl radical bound viaa sulfur atom to the remainder of the molecule).

Examples for C₁-C₆-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, neo-pentoxy,n-hexoxy, and position isomers thereof.

Examples for C₁-C₂₀-alkoxy are, apart those mentioned above forC₁-C₆-alkoxy, n-heptoxy, n-octyloxy, n-nonyloxy, n-decyloxy,n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy,n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy,n-nonadecyloxy, n-docosyloxy and position isomers thereof.

Examples for C₁-C₆-alkylthio are methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio,n-pentylthio, neo-pentylthio, n-hexylthio, and position isomers thereof.

Examples for C₁-C₂₀-alkylthio are, apart those mentioned above forC₁-C₆-alkyl, n-heptylthio, n-octylthio, 2-ethylhexylthio, n-nonylthio,n-decylthio, 2-propylheptylthio, n-undecylthio, n-dodecylthio,n-tridecylthio, n-tetradecylthio, n-hexadecylthio, n-heptadecylthio,n-octadecylthio, n-nonadecylthio, n-eicosylthio and position isomersthereof.

In the context of the present invention, the term “cycloalkyl” denotes amono-, bi- or tricyclic hydrocarbon radical having usually from 3 to 20(“C₃-C₂₀-cycloalkyl”), preferably 3 to 12 (“C₃-C₁₂-cycloalkyl”), morepreferably 3 to 10 (“C₃-C₁₀-cycloalkyl”), in particular 3 to 8(“C₃-C₈-cycloalkyl”), e.g. 5 to 8 (“C₅-C₈-cycloalkyl”), carbon atomssuch as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl,bicyclo[2.2.2]octyl or adamantyl.

Preferably, the term cycloalkyl denotes a monocyclic hydrocarbonradical.

Examples for C₃-C₈-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl and cyclooctyl.

Substituted cycloalkyl groups may, depending on the ring size, have oneor more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These arepreferably each independently selected from alkyl, alkoxy, alkylthio,cycloalkyl, aryl, fluorine, chlorine, bromine, hydroxyl, mercapto,cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate,alkylcarbonyloxy, carbamoyl, SO₃H, sulfonate, sulfamino, sulfamide,amidino, NE³E⁴, where E³ and E⁴ are each independently hydrogen, alkyl,cycloalkyl or aryl. In the case of substitution, the cycloalkyl groupspreferably bear one or more, for example one, two, three, four or five,C₁-C₆-alkyl groups.

The above remarks regarding cycloalkyl also apply to the cycloalkylmoiety in cycloalkoxy (a cycloalkyl radical bound via an oxygen atom tothe remainder of the molecule) and cycloalkylthio (=cycloalkylsulfanyl;a cycloalkyl radical bound via a sulfur atom to the remainder of themolecule).

Examples for C₃-C₈-cycloalkoxy are cyclopropoxy, cyclobutoxy,cyclopentoxy, cyclohexoxy, cycloheptoxy and cyclooctoxy.

Examples for C₃-C₈-cycloalkylthio are cyclopropylthio, cyclobutylthio,cyclopentylthio, cyclohexylthio, cycloheptylthio and cyclooctylthio.

In the context of the present invention, the term “aryl” refers to mono-or polycyclic aromatic hydrocarbon radicals. Aryl usually is an aromaticradical having 6 to 24 carbon atoms, preferably 6 to 20 carbon atoms,especially 6 to 14 carbon atoms as ring members. Aryl is preferablyphenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl,naphthacenyl, chrysenyl, pyrenyl, coronenyl, perylenyl, etc., and morepreferably phenyl or naphthyl. Specifically, aryl is phenyl.

Substituted aryls may, depending on the number and size of their ringsystems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5)substituents. These are preferably each independently selected fromalkyl, alkoxy, alkylthio, cycloalkyl, aryl, fluorine, chlorine, bromine,hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH,carboxylate, alkylcarbonyloxy, carbamoyl, SO₃H, sulfonate, sulfamino,sulfamide, amidino, NE⁵E⁶, where E⁵ and E⁶ are each independentlyhydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Thealkyl, alkoxy, alkylthio, cycloalkyl and aryl substituents on the arylmay in turn be unsubstituted or substituted. Reference is made to thesubstituents mentioned above for these groups. The substituents on thearyl are preferably selected from alkyl and alkoxy. Substituted aryl ismore preferably substituted phenyl which generally bears 1, 2, 3, 4 or5, preferably 1, 2 or 3, substituents.

Substituted aryl is preferably aryl substituted by at least one alkylgroup (“alkaryl”, also referred to hereinafter as alkylaryl). Alkarylgroups may, depending on the size of the aromatic ring system, have oneor more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkylsubstituents. The alkyl substituents may be unsubstituted orsubstituted. In this regard, reference is made to the above statementsregarding unsubstituted and substituted alkyl. In a preferredembodiment, the alkaryl groups have exclusively unsubstituted alkylsubstituents. Alkaryl is preferably phenyl which bears 1, 2, 3, 4 or 5,preferably 1, 2 or 3, more preferably 1 or 2, alkyl substituents.

Aryl which bears one or more radicals is, for example, 2-, 3- and4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3-and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-,3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl,2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-,3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3-and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl.

The above remarks regarding aryl also apply to the aryl moiety inaryloxy (an aryl radical bound via an oxygen atom to the remainder ofthe molecule) and arylthio (=arylsulfanyl; an aryl radical bound via asulfur atom to the remainder of the molecule).

The term alkylene refers to a linear or branched diradical of an alkane(or, in other words, a divalent alkyl radical).

C₂-C₃-Alkylene is a linear or branched divalent alkyl radical having 2or 3 carbon atoms. Examples are 1,1-ethylene [CH(CH₃)], 1,2-ethylene(CH₂CH₂), 1,1-propylene [CH(CH₂CH₃)], 2,2-propylene [—C(CH₃)₂—],1,2-propylene [CH₂CH(CH₃)] or 1,3-propylene (CH₂CH₂CH₂).

C₁-C₃-Alkylene is a linear or branched divalent alkyl radical having 1,2 or 3 carbon atoms. Examples are, apart those mentioned above forC₂-C₃-alkylene, also methylene (CH₂).

C₂-C₆-Alkylene is a linear or branched divalent alkyl radical having 2,3, 4, 5 or 6 carbon atoms. Examples are, apart those mentioned above forC₂-C₃-alkylene, n-butylene [(CH₂)₄], [(CH₂)₃CH(CH₃)], (CH₂CH(CH₃)CH₂),[CH(CH₂CH₂CH₃)], [CH₂CH(CH₂CH₃)], [—C(CH₃)₂CH₂—], n-pentylene [(CH₂)₅],n-hexylene [hexamethylene; (CH₂)₆] and position isomers thereof.

C₁-C₆-Alkylene is a linear or branched divalent alkyl radical having 1,2, 3, 4, 5 or 6 carbon atoms. Examples are, apart from the examplesmentioned above for C₂-C₆-alkylene, also methylene (CH₂).

C₁-C₃₀-Alkylene is a linear or branched divalent alkyl radical having 1to 30 carbon atoms. Examples for C₁-C₃₀-alkylene are, apart from theexamples mentioned above for C₁-C₆-alkylene, diradicals (CH₂)_(x),wherein x is an integer from 7 to 30, such as heptamethylene,octamethylene, nonamethylene, decamethylene and the like, and positionisomers thereof.

C₄-C₁₂-Alkylene is a linear or branched divalent alkyl radical having 4to 12 carbon atoms. Examples for C₄-C₁₂-alkylene are n-butylene[(CH₂)₄], [(CH₂)₃CH(CH₃)], (CH₂CH(CH₃)CH₂), [CH(CH₂CH₂CH₃)],[CH₂CH(CH₂CH₃)], [—C(CH₃)₂CH₂—], n-pentylene [(CH₂)₅], n-hexylene[hexamethylene; (CH₂)₆], heptamethylene, octamethylene, nonamethylene,decamethylene, undecamethylene, dodecamethylene, and position isomersthereof.

C₄-C₂₀-Alkylene is a linear or branched divalent alkyl radical having 4to 20 carbon atoms. Examples for C₄-C₂₀-alkylene are, apart from theexamples mentioned above for C₄-C₁₂-alkylene, diradicals (CH₂)_(x),wherein x is an integer from 13 to 20, and position isomers thereof.

C₃-C₂₀-Alkylene is a linear or branched divalent alkyl radical having 3to 20 carbon atoms. Examples for C₃-C₂₀-alkylene are, apart from theexamples mentioned above for C₄-C₁₂-alkylene, 1,1-propylene[CH(CH₂CH₃)], 2,2-propylene [—C(CH₃)₂—], 1,2-propylene [CH₂CH(CH₃)] or1,3-propylene (CH₂CH₂CH₂).

Alkenylene is a linear or branched aliphatic mono- or poly-, e.g. mono-or di-, olefinically unsaturated divalent radical having, for example, 2to 20 or 2 to 10 or 4 to 8 carbon atoms. If the radical comprises morethan one carbon-carbon double bond, these are preferably not vicinal,i.e. not allenic.

Alkynylene is a linear or branched aliphatic divalent radical having,for example, 2 to 20 or 2 to 10 or 4 to 8 carbon atoms which comprisesone or more, e.g. 1 or 2, carbon-carbon triple bonds.

C₅-C₈-Cycloalkylene is a divalent monocyclic, saturated hydrocarbongroup having 5 to 8 carbon ring members. Examples arecyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,2-diyl,cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, cycloheptane-1,2-diyl,cycloheptane-1,3-diyl, cycloheptane-1,4-diyl, cyclooctane-1,2-diyl,cyclooctane-1,3-diyl, cyclooctane-1,4-diyl and cyclooctane-1,5-diyl.

Carboxylate and sulfonate respectively represent a derivative of acarboxylic acid function and a sulfonic acid function, especially ametal carboxylate or sulfonate, a carboxylic ester or sulfonic esterfunction or a carboxamide or sulfonamide function.

In context of the radical A (see below) being an alkylene group whichmay be substituted by a carboxylate group, this term is limited to acarboxylate anion (COO⁻).

The expression “halogen” denotes in each case fluorine, bromine,chlorine or iodine, particularly chlorine, bromide or iodine.

Imidazolium Compound

The following general definition of the imidazolium compounds employedaccording to the invention applies to all concrete compositionscomprising at least one imidazolium compound mentioned in thisapplication. The following general definition of the imidazoliumcompounds also applies to all concrete uses of those compounds mentionedin this application. Possible differences (if any) are mentioned foreach individual composition or use.

Suitable imidazolium compounds for the biocide compositions according tothe invention and methods for their production are described in WO2010/072571 which is incorporated herein by reference. Accordingly, theimidazolium compounds can be obtained by a polycondensation reaction ofat least one α-dicarbonyl compound, at least one aldehyde, at least oneamino compound having at least two primary amino groups and at least oneprotic acid as essential starting materials. In a polycondensation,polymerization occurs with elimination of a low molecular weightcompound, such as water or alcohol. In the present case, water iseliminated. When the carbonyl groups of the α-dicarbonyl compound arepresent completely or partly as ketal and/or the aldehyde group of thealdehyde is present as acetal or hemiacetal, an alcohol iscorrespondingly eliminated instead of water.

a) α-Dicarbonyl Compound

The α-dicarbonyl compound is preferably selected from compounds of theformula (I)

R¹—CO—CO—R²  (I)

whereinR¹ and R² are independently selected from hydrogen and in each caseunsubstituted or substituted alkyl, alkoxy, alkylthio, cycloalkyl,cycloalkoxy, cycloalkylthio, aryl, aryloxy, arylthio. Preferably, R¹ andR² are independently selected from hydrogen and in each caseunsubstituted or substituted alkyl, cycloalkyl and aryl and morepreferably from hydrogen and in each case unsubstituted or substitutedC₁-C₂₀-alkyl, C₃-C₈-cycloalkyl and aryl.

The α-dicarbonyl compound a) preferably comprises or consists ofglyoxal. Thus, in particular R¹ and R² are hydrogen.

The aldehyde or keto group of the compound a) can also be present ashemiacetal, acetal, hemiketal or ketal, preferably of a lower alcohol,in particular a C₁-C₁₀-alkanol. In this case, the alcohol is eliminatedin the condensation reaction forming the imidazolium compound.

Preferably, the compound a) is not employed in form of a hemiacetal,acetal, hemiketal or ketal.

b) Aldehyde

The aldehyde b) is preferably selected from compounds of the formula(II)

R³—CHO  (II)

whereinR³ is selected from hydrogen, alkyl, cycloalkyl and aryl.

Preferably, R³ is selected from hydrogen, C₁-C₂₀-alkyl,C₃-C₈-cycloalkyl, optionally substituted aryl and a radical of theformula —CH₂O—CH₂CH₂_(x)—OR^(a), wherein x is 1, 2, 3, 4, 5 or 6 andR^(a) is hydrogen or C₁-C₄-alkyl, and is more preferably selected fromhydrogen, C₁-C₂₀-alkyl, a group —CH₂O—CH₂CH₂_(x)—OR^(a), wherein x is1, 2, 3, 4, 5 or 6 and R^(a) is hydrogen or C₁-C₄-alkyl and phenyl whichmay be substituted by 1, 2, 3, 4 or 5 radicals selected fromC₁-C₂₀-alkyl, C₁-C₆-haloalkyl, C₁-C₂₀-alkoxy, C₁-C₆-haloalkoxy andNR′R″, where R′ and R′R″ are, independently of each other, selected fromhydrogen and C₁-C₆-alkyl.

Suitable aldehydes are e.g. formaldehyde, acetaldehyde, propionaldehyde,butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal,undecanal, dodecanal, tridecanal, tetradecanal and the higher homologswith up to 20 carbon atoms, benzaldehyde, substituted benzaldehydes,such as 2-, 3- or 4-methylbenzaldehyde, 2-, 3- or4-trifluoromethylbenzaldehyde or 2-, 3- or 4-methoxybenzaldehyde, andaldehydes of formula CH(═O)—CH₂O—CH₂CH₂_(x)—OR^(a), wherein x is 1, 2,3, 4, 5 or 6 and R^(a) is hydrogen or C₁-C₄-alkyl, derived from apolyethylene glycol or polythyleneglycol monoether of formulaHOCH₂CH₂O—CH₂CH₂_(x)—OR^(a), wherein x is 1, 2, 3, 4, 5 or 6 and R^(a)is hydrogen or C₁-C₄-alkyl, in which one CH₂OH group in oxidized to aCHO group.

The aldehyde group of the aldehyde b) can also be present as hemiacetalor acetal, preferably as hemiacetal or acetal of a lower alcohol, inparticular a C₁-C₁₀-alkanol. In this case, the alcohol is eliminated inthe condensation reaction forming the imidazolium compound.

The aldehyde group is preferably not present as hemiacetal or acetal.

Preferably, component b) comprises or consists of a formaldehyde source.Thus, in particular R³ is hydrogen. Suitable formaldehyde sources areformaldehyde, formaldehyde oligomers (e.g. trioxane) and polymers offormaldehyde (e.g. paraformaldehyde). More preferably, component b)comprises or consists of formaldehyde. In a suitable embodiment, theformaldehyde is employed as an aqueous solution (formalin solution).

Alternatively, the aldehyde is preferably selected from benzaldehyde andan aldehyde of formula R³—CHO, where R³ is C₁-C₂₀-alkyl, more preferablyfrom acetaldehyde, propionaldehyde, butanal, pentanal, hexanal,heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal,tetradecanal and the higher homologs with up to 20 carbon atoms, andbenzaldehyde.

Specifically, the aldehyde is selected from formaldehyde (or aformaldehyde source), dodecanal and benzaldehyde and is veryspecifically formaldehyde (or a formaldehyde source).

c) Amino Compound Having at Least Two Primary Amino Groups

The amino compound is preferably selected from compounds of the formula(III)

A(NH₂)_(m)  (III)

whereinm is an integer greater than or equal to 2, andA is an m-valent organic radical.

In the formula (III), m indicates the number of primary amino groupsbound to the group A. m can assume very large values, e.g. m can be aninteger from 2 to 10 000, in particular from 2 to 5000. Very high valuesof m are present, e.g. if the compound c) of the formula (III) comprisesa nitrogen-comprising polymer.

If only amino compounds c) of the formula (III) are employed, wherein mis 2 (diamines), the obtained imidazolium compounds are linear.

If at least one amino compound c) of the formula (III) is employed,wherein m is greater than 2, the obtained imidazolium compounds arebranched.

In a preferred embodiment, m is an integer from 2 to 6, in particularfrom 2 to 4. More preferably, m is 2 (diamine) or m is 3 (triamine). Inparticular, m is 2.

In alternative embodiment, component c) comprises at least one aminocompound having two primary amino groups and at least one amino compoundhaving three primary amino groups. In this embodiment, m is a realnumber in a range of greater than 2 and less than 3.

The group A can be, in particular, a hydrocarbon group, which can besubstituted or interrupted by functional groups comprising heteroatoms.

In a preferred embodiment, component c) is selected from

-   -   amines of the formula 1

H₂N-A-NH₂  (1)

-   -   wherein    -   A is a divalent aliphatic, alicyclic, aliphatic-alicyclic,        aromatic or araliphatic radical, where the aliphatic moieties in        the aforementioned aliphatic, aliphatic-alicyclic or araliphatic        radicals may be interrupted by one or more nonadjacent groups        which are selected from —O—, —S— and —N(R^(b))—, where R^(b) is        selected from hydrogen, C₁-C₂₀-alkyl and a group        CH₂CH₂—O_(y)—R^(c), wherein y is 1, 2, 3, 4, 5 or 6 and R^(c)        is hydrogen or C₁-C₄-alkyl; where alicyclic or aromatic moieties        in the aforementioned alicyclic, aliphatic-alicyclic, aromatic        or araliphatic radicals may be substituted by 1, 2, 3 or 4        radicals selected from C₁-C₂₀-alkyl, C₁-C₂₀-alkoxy, a radical of        the formula —O—CH₂CH₂O]_(z)—R^(d), where R^(d) is hydrogen or        C₁-C₄-alkyl and z is 1, 2, 3, 4, 5 or 6; carboxyl and        carboxylate, and where the aliphatic moieties in the        aforementioned aliphatic, aliphatic-alicyclic or araliphatic        radicals may be substituted by 1, 2, 3 or 4 radicals selected        from C₁-C₂₀-alkoxy, a radical of the formula        —OCH₂CH₂O]_(z)—R^(d), where R^(d) is hydrogen or C₁-C₄-alkyl        and z is 1, 2, 3, 4, 5 or 6, carboxyl and carboxylate; with the        proviso that the aromatic or araliphatic radicals do not contain        1,4-bound phenylene rings;    -   amines of the formula 2

in which

-   Y is CR^(C), N, C₂-C₆-alkyl or C₃-C₆-cycloalkyl;-   E₁, E₂ and E₃, independently of each other, are a single bond,    C₁-C₁₀-alkylene, —NR^(D)—C₂-C₁₀-alkylene or —O—C₁-C₁₀-alkylene, with    the proviso that E₁, E₂ and E₃ are not a single bond and are not    —NR^(D)—C₂-C₁₀-alkylene when Y is N;-   R^(C) is H, C₂-C₄-hydroxyalkyl or C₁-C₄-alkoxy and is preferably H,    C₁-C₄-alkyl or C₁-C₄-alkoxy; and-   R^(B) and R^(D), independently of each other, are H, C₁-C₄-alkyl,    C₂-C₄-hydroxyalkyl or C₁-C₄-alkoxy and are preferably H, C₁-C₄-alkyl    or C₁-C₄-alkoxy; and    -   mixtures thereof.

Divalent aliphatic radicals are those which comprise no cycloaliphatic,aromatic or heterocyclic constituents. Examples are alkylene, alkenyleneand alkynylene radicals.

Divalent alicyclic radicals can comprise one or more, e.g. one or two,alicyclic radicals;

however, they comprise no aromatic or heterocyclic constituents. Thealicyclic radicals can be substituted by aliphatic radicals, but bondingsites for the NH₂ groups are located on the alicyclic radical.

Divalent aliphatic-alicyclic radicals comprise not only at least onedivalent aliphatic radical but also at least one divalent alicyclicradical, it being possible for the two bonding sites for the NH₂ groupsto both either be located on the alicyclic radical(s) or both on thealiphatic radical(s) or one on an aliphatic radical and the other on analicyclic radical.

Divalent aromatic radicals can comprise one or more, e.g. one or two,aromatic radicals; however, they comprise no alicyclic or heterocyclicconstituents. The aromatic radicals can be substituted by aliphaticradicals, but both bonding sites for the NH₂ groups are located on thearomatic radical(s).

Divalent araliphatic radicals comprise not only at least one divalentaliphatic radical but also at least one divalent aromatic radical, itbeing possible for the two bonding sites for the NH₂ groups to belocated either both on the aromatic radical(s) or both on the aliphaticradical(s) or one on an aliphatic radical and the other on an aromaticradical.

Preferably, the divalent aliphatic radicals A are selected from linearand branched C₁-C₃₀-alkylene which may be interrupted by one or morenonadjacent groups which are selected from —O—, —S— and —N(R^(b))—,where R^(b) is selected from hydrogen, C₁-C₂₀-alkyl and a groupCH₂CH₂—O_(y)R^(c), wherein y is 1, 2, 3, 4, 5 or 6 and R^(c) ishydrogen or C₁-C₄-alkyl; and/or may be substituted by 1, 2, 3 or 4radicals selected from C₁-C₂₀-alkoxy, a radical of the formula—OCH₂CH₂O]_(z)—R^(d), where R^(d) is hydrogen or C₁-C₄-alkyl and z is1, 2, 3, 4, 5 or 6, carboxyl and carboxylate.

More preferably, the divalent aliphatic radical A is linear or branchedC₂-C₂₀-alkylene, even more preferably linear or branchedC₃-C₂₀-alkylene, particularly preferably linear or branchedC₄-C₂₀-alkylene and in particular linear or branched C₄-C₁₂-alkylene;specifically a linear C₄-C₁₂-alkylene. The alkylene chain may carry acarboxyl or carboxylate group. Preferably, the alkylene biradical islinear. Examples of suitable amines in which the radical A has thismeaning (C₂-C₂₀-alkylene) are 1,2-ethylenediamine, 1,2- and1,3-propylenediamine, 2,2-dimethyl-1,3-propanediamine,1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine,heptamethylenediamine, octamethylenediamine, nonamethylenediamine,decamethylenediamine, undecamethylenediamine, dodecamethylenediamine,tridecamethylenediamine, tetradecamethylenediamine,pentadecamethylenediamine, hexadecamethylenediamine,heptadecamethylenediamine, octadecamethylenediamine,nonadecamethylenediamine, eicosamethylenediamine,2-butyl-2-ethyl-1,5-pentamethylenediamine, 2,2,4- or2,4,4-trimethyl-1,6-hexamethylenediamine, 1,5-diamino-2-methylpentane,1,4-diamino-4-methylpentane and the like. Among these, preference isgiven to 1,4-butylene diamine, 1,5-pentylene diamine, 1,6-hexylenediamine, 1,8-octylene diamine, 1,12-dodecylenediamine and mixturesthereof. Also preferred are the carboxyl- or carboxylate-substitutedalkylene diamines of formulae NH₂—CH(COOH)CH₂CH₂CH₂—NH₂ andNH₂—CH(COO⁻)CH₂CH₂CH₂—NH₂.

In an alternatively more preferred embodiment, the divalent aliphaticradical A is a group B—X_(k)—B— in which each X independently is —O—,—S— or —N(R^(b))—, where R^(b) is selected from hydrogen, C₁-C₂₀-alkyland a group CH₂CH₂—O_(y)—R^(c), wherein y is 1, 2, 3, 4, 5 or 6 andR^(c) is hydrogen or C₁-C₄-alkyl, preferably O, each B independently isC₂-C₆-alkylene, preferably C₂-C₃-alkylene; and k is an integer from 1 to100, preferably 1 to 10 and more preferably 2 to 4. Examples of suitableamines in which the radical A has this meaning are amine-terminatedpolyoxyalkylene polyols, for example Jeff-Amines, such as1,8-diamino-3,6-dioxaoctan, 1,13-diamino-4,7,10-trioxatridecan,4,9-dioxadodecane-1,12-diamine and 4,7,10-trioxatridecane-1,13-diamine,or else more regular amine-terminated polyoxyalkylenediols(amine-terminated polyalkylene glycols; amine-terminated polyalkyleneoxides), such as amine-terminated polyethylene glycols, amine-terminatedpolypropylene glycols or amine-terminated polybutylene glycols. Thethree last-mentioned amines (amine-terminated polyalkylene glycols)preferably have a molecular weight of from 100 to 3000 g/mol. Amongthese, preference is given to amines NH₂—[CH₂CH₂O]_(x)—CH₂CH₂—NH₂ with xbeing 2 or 3, preferably 2, andNH₂—CH₂CH₂CH₂—[CH₂CH₂O]_(x)—CH₂CH₂CH₂—NH₂ with x being 2 or 3,preferably 2.

Preferably, the divalent alicyclic radicals A are selected fromC₅-C₈-cycloalkylene which may carry 1, 2, 3 or 4 C₁-C₄-alkyl radicals.Examples of suitable amines in which the radical A has this meaning arecyclopentylenediamine, such as 1,2-diaminocyclopentane or1,3-diaminocyclopentane, cyclohexylenediamine, such as1,2-diaminocyclohexane, 1,3-diaminocyclohexane or1,4-diaminocyclohexane, 1-methyl-2,4-diaminocyclohexane,1-methyl-2,6-diaminocyclohexane, cycloheptylenediamine, such as1,2-diaminocycloheptane, 1,3-diaminocycloheptane or1,4-diaminocycloheptane, and cyclooctylenediamine, such as1,2-diaminocyclooctane, 1,3-diaminocyclooctane, 1,4-diaminocyclooctaneor 1,5-diaminocyclooctane. The amino groups (NH₂ groups) may be in thecis or trans position relative to one another.

Preferably, the divalent aliphatic-alicyclic radicals A are selectedfrom C₁-C₄-alkylene-C₅-C₈-cycloalkylene,C₅-C₈-cycloalkylene-C₁-C₄alkylene-C₅-C₈-cycloalkylene andC₁-C₄-alkylene-C₅-C₈-cycloalkylene-C₁-C₄-alkylene, where thecycloalkylene radicals may carry 1, 2, 3 or 4 C₁-C₄-alkyl radicals.Examples of suitable amines in which the radical A has this meaning arediaminodicyclohexylmethane, such as bis(4-aminocyclohexyl)methane orbis(3-aminocyclohexyl)methane; isophoronediamine,bis(aminomethyl)cyclohexane, such as 1,1-bis(aminomethyl)cyclohexane,1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or1,4-bis(aminomethyl)cyclohexane, 2-aminopropylcyclohexylamine,3(4)-aminomethyl-1-methylcyclohexylamine,2-(2-amino-propyl)-cyclohexylamine and the like. The groups bonded tothe alicyclic radical can in each case assume any desired position(cis/trans) relative to one another.

Preferably, the divalent aromatic radicals A are selected from1,2-phenylene, 1,3-phenylene, naphthylene and biphenylene, with thephenylene radicals possibly carrying 1, 2, 3 or 4 radicals selected fromC₁-C₂₀-alkyl, C₁-C₂₀-alkoxy and a radical of the formula—OCH₂CH₂O]_(x)—R^(d), where R_(d) is hydrogen or C₁-C₄-alkyl and z is1, 2, 3, 4, 5 or 6. Examples of suitable amines in which the radical Ahas this meaning are o-phenylenediamine, m-phenylenediamine,tolylenediamine, such as o-, m- and p-tolylenediamine, xylylenediamine,and naphthylenediamine, such as 1,2-, 1,3-, 1,4-, 1,5-, 1,8-, 2,3-, 2,6-and 2,7-naphthylene.

Preferably, the divalent araliphatic radicals A are selected fromphenylene-C₁-C₄-alkylene, phenylene-C₁-C₄-alkylene-phenylene andC₁-C₄-alkylene-phenylene-C₁-C₄-alkylene, with the phenylene radicalspossibly carrying 1, 2, 3 or 4 radicals selected from C₁-C₂₀-alkyl,C₁-C₂₀-alkoxy and a radical of the formula —OCH₂CH₂O]_(z)—R^(d), whereR^(d) is hydrogen or C₁-C₄-alkyl and z is 1, 2, 3, 4, 5 or 6. Examplesof suitable amines in which the radical A has this meaning arediaminodiphenylmethane, such as 2,2′-, 3,3′- and4,4′-diaminodiphenylmethane, 3-aminomethyl-benzylamine and the like.

Examples for amines 2 are

compounds of the formula (2.A)

wherein R⁵, R⁶ and R⁷ are each, independently of one another, a C₁-C₁₀alkylene group, particularly preferably a C₂-C₆-alkylene group;such as N,N-bis(3-aminopropyl)ethylenediamine,N,N-bis(3-aminopropyl)propane-1,3-diamine,N,N-bis(3-aminopropyl)butane-1,4-diamine, tris(2-aminoethyl)amine,tris(2-aminopropyl)amine, tris(3-aminopropyl)amine,tris(2-aminobutyl)amine, tris(3-aminobutyl)amine,tris(4-aminobutyl)amine, tris(5-aminopentyl)amine andtris(6-aminohexyl)amine. In a preferred embodiment, R⁵, R⁶ and R⁷ havethe same meaning. A preferred compound (2.A) is tris(2-aminoethyl)amine(R⁵=R⁶=R⁷=ethylene).

Further examples of amines 2 are trisaminohexane, trisaminononane,4-aminomethyl-1,8-octamethylenediamine and the like.

Further examples of amines 2 are the compounds of following structures(2.B) or (2.C):

Further examples of amines 2 are amines of the formula 2, wherein Y isCR^(C), where R^(C) is H or C₁-C₄-alkyl, and E₁, E₂ and E₃,independently of each other, are —O—C₁-C₆-alkylene, preferably—O—CH₂CH₂CH(CH₃)—. Among these, preference is given to a compoundwherein Y is CR^(C), where R^(C) is ethyl, and E¹, E₂ and E₃ are—O—CH₂CH₂CH(CH₃)—.

Among the above compounds 2, preference is given to the amine of theformula 2, wherein Y is CR^(C), where R^(C) is ethyl, and E₁, E₂ and E₃are —O—CH₂CH₂CH(CH₃)—.

In particular, the amine c) is selected from:

-   -   compounds of the formula H₂N—(CH₂)_(m)—NH₂, wherein m is an        integer of 3 to 20, preferably 4 to 20, more preferably 4 to 12,        where a CH₂ group may be substituted by a carboxyl or        carboxylate group, such as 1,3-propylenediamine,        1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine,        heptamethylenediamine, octamethylenediamine,        nonamethylenediamine, decamethylenediamine,        undecamethylenediamine, dodecamethylenediamine,        tridecamethylenediamine, tetradecamethylenediamine,        pentadecamethylenediamine, hexadecamethylenediamine,        heptadecamethylenediamine, octadecamethylenediamine,        nonadecamethylenediamine, eicosamethylenediamine, the carboxyl-        or carboxylate-substituted alkylene diamines of formulae        NH₂—CH(COOH)CH₂CH₂CH₂—NH₂ or NH₂—CH(COO⁻)CH₂CH₂CH₂—NH₂;        especially 1,4-butylene diamine, 1,5-pentylene diamine,        1,6-hexylene diamine, 1,8-octylene diamine,        1,12-dodecylenediamine and the carboxyl- or        carboxylate-substituted alkylene diamines of formulae        NH₂—CH(COOH)CH₂CH₂CH₂—NH₂ or NH₂—CH(COO⁻)CH₂CH₂CH₂—NH₂;    -   compounds of the formula NH₂B—X_(k)—B—NH₂; in which each X        independently is —O—, —S— or —N(R^(b))—, where R^(b) is selected        from hydrogen, C₁-C₂₀-alkyl and a group CH₂CH₂—O_(y)—R^(c),        wherein y is 1, 2, 3, 4, 5 or 6 and R^(c) is hydrogen or        C₁-C₄-alkyl, preferably O; each B independently is        C₂-C₆-alkylene, preferably C₂-C₃-alkylene; and k is an integer        from 1 to 100, preferably 1 to 10, more preferably 2 to 4, such        as 1,8-diamino-3,6-dioxaoctan,        1,13-diamino-4,7,10-trioxatridecan,        4,9-dioxadodecane-1,12-diamine and        4,7,10-trioxatridecane-1,13-diamine, or else more regular        amine-terminated polyoxyalkylenediols (amine-terminated        polyalkylene glycols; amine-terminated polyalkylene oxides),        such as amine-terminated polyethylene glycols, amine-terminated        polypropylene glycols or amine-terminated polybutylene glycols;        especially NH₂—[CH₂CH₂O]_(x)—CH₂CH₂—NH₂ with x being 2 or 3,        preferably 2, and NH₂—CH₂CH₂CH₂—[CH₂CH₂O]_(x)—CH₂CH₂CH₂—NH₂ with        x being 2 or 3, preferably 2;    -   bis(4-aminocyclohexyl)methane, bis(3-aminocyclohexyl)methane,        isophoronediamine, 1,1-bis(aminomethyl)cyclohexane,        1,2-bis(aminomethyl)cyclohexane,        1,3-bis(aminomethyl)cyclohexane,        1,4-bis(aminomethyl)cyclohexane, 2-aminopropylcyclohexylamine,        3(4)-aminomethyl-1-methylcyclohexylamine,        2-(2-amino-propyl)-cyclohexylamine; especially        bis(4-aminocyclohexyl)methane, bis(3-aminocyclohexyl)methane,        isophoronediamine; 3-aminomethyl-benzylamine;    -   amines of the formula 2, wherein Y is CR^(C), where R^(C) is H        or C₁-C₄-alkyl, and E₁, E₂ and E₃, independently of each other,        are —O—C₁-C₆-alkylene, preferably —O—CH₂CH₂CH(CH₃)—; especially        the amine of the formula 2, wherein Y is CR^(C), where R^(C) is        ethyl, and E₁, E₂ and E₃ are —O—CH₂CH₂CH(CH₃)—; and    -   mixtures thereof.

It is of course also possible to use in the biocide compositions of theinvention imidazolium compounds that are obtained from a mixture of twoor more than two different amino compounds c). If an amine of formula 2is used, it is even preferred to use it in combination with a diamineA(NH₂)_(m) with m being 2. In a preferred embodiment, the mixture ofamino compounds c) comprises at least two amino compounds havingdifferent numbers of primary amino groups. The use of diamines (m=2) inadmixture with amino compounds having more than two primary amino groups(m>2), e.g. triamines, enables the desired degree of crosslinking ordegree of branching to be set via the proportion of amines with m=2 toamines m>2.

Preferred mixtures of amino compounds c) are the following:

-   -   tris(2-aminoethyl)amine and ethylene diamine    -   tris(2-aminoethyl)amine and 1,3-propylene diamine    -   tris(2-aminoethyl)amine and 1,4-butylenediamine    -   tris(2-aminoethyl)amine and 1,5-pentylene diamine    -   tris(2-aminoethyl)amine and 1,6-hexylene diamine    -   the amine of the formula 2, wherein Y is CR^(C), where R^(C) is        ethyl, and E₁, E₂ and E₃ are —O—CH₂CH₂CH(CH₃)— and        1,4-butylenediamine.

In a preferred embodiment, the amino compound c) has a molecular weightof less than 10 000 g/mol, particularly preferably less than 5000 g/mol,very particularly preferably less than 1000 g/mol, in particular lessthan 500 g/mol.

Possible diamines and triamines are, in particular, compounds having amolecular weight of from 60 to 500 g/mol or from 60 to 250 g/mol.

In a further preferred embodiment, component c) is selected fromnitrogen-comprising polymers. Preferably, component c) is selected frompolyvinylamine polymers.

Suitable polyvinylamine polymers are obtainable by free radicalpolymerization of ethylenically unsaturated monomers having a nitrogencontaining group that can be transferred into a primary amino group. Inparticular, such monomers are selected from vinylcarboxamides whichcomprise amido groups that are capable of hydrolysis under formation ofprimary amino groups.

Suitable polyvinylamine polymers c) are described inter alia in U.S.Pat. No. 4,421,602, U.S. Pat. No. 5,334,287, EP-A 216 387, U.S. Pat. No.5,981,689, WO 00/63295, U.S. Pat. No. 6,121,409 and U.S. Pat. No.6,132,558. The teaching of those documents is incorporated herein byreference. They are prepared in general by hydrolysis of polymerscomprising N-vinylcarboxamide units. These polymers contain inpolymerized form monomers selected from e.g. N-vinylformamide,N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide,N-vinyl-N-ethylacetamide, N-vinylpropionamide and mixtures thereof. Itis possible to use comonomers from different monomer classes. Preferredpolyvinylamines polymers c) are homopolymers of N-vinylformamide.

The homo- and copolymers which comprise N-vinylcarboxamide unitsincorporated in the form of polymerized units can be partly orcompletely hydrolyzed by known methods. The degree of hydrolysis isgenerally in a range from 1 to 100 mol %, preferably from 10 to 99 mol%, particularly preferably from 20 to 95 mol % and especially preferablyfrom 30 to 90 mol %. The degree of hydrolysis corresponds to the contentof primary vinylamine groups in the polymers, in mol %. The hydrolysisof the polymers described above is effected by known processes, by theaction of acids (e.g. mineral acids, such as sulfuric acid, hydrochloricacid or phosphoric acid, carboxylic acids, such as formic acid or aceticacid, or sulfonic acids or phosphonic acids), bases or enzymes, asdescribed, for example, in DE-A 31 28 478 and U.S. Pat. No. 6,132,558.With the use of acids as hydrolysis agents, the vinylamine units of thepolymers are present as an ammonium salt, while the free amino groupsform in the hydrolysis with bases.

Suitable polyvinylamine polymers c) preferably have a number averagemolecular weight in a range of from 220 to 1 000 000, preferably from440 to 100 000 and in particular 750 to 50 000.

Suitable poly(alkyleneimines) polymers c) include the homopolymers ofethyleneimine (aziridine) or its higher homologues, the copolymers ofethyleneimine or its higher homologues with further monomers, and alsothe graft polymers, e.g. of polyamidoamines or polyvinylamines, withethyleneimine or its higher homologues. The poly(alkyleneimines) can becrosslinked or uncrosslinked. They can be modified, e.g. by reactionwith alkylene oxides, dialkyl or alkylene carbonates or C₁- toC₄-carboxylic acids or derivatives of C₁- to C₄-carboxylic acids.

Suitable poly(alkyleneimines) are obtainable by customary processesknown to the person skilled in the art and are commercially available.Suitable poly(alkyleneimine)s are all polymers which are obtainable bycationically initiated polymerization of alkyleneimines and/orN-substituted alkyleneimines. Preferred poly(alkyleneimines) arepolyethyleneimines. They are obtainable by cationically initiatedpolymerization of ethyleneimine (aziridine) and/or N-substitutedaziridines.

Poly(alkyleneimines) useful as component c) also include the polymers ofhigher homologues of ethyleneimine, such as propyleneimine(2-methylaziridine), 1- or 2-butyleneimine (2-ethylaziridine or2,3-dimethylaziridine). The poly(alkyleneimines) are preferablyhomopolymers of ethyleneimine.

Catalysts which can be used for the cationic polymerization ofalkyleneimines are, for example, Brønsted acids, such as sulfuric acid,phosphoric acid, p-toluenesulfonic acid, or carboxylic acids, such asformic acid, acetic acid or propionic acid, or Lewis acids, such ashalides, for example zinc chloride or alkyl halides, such as methylchloride, ethyl chloride, benzyl chloride or ethylene chloride. Suitablepolyethyleneimines can also be obtained by reaction of ethylene chloridewith ammonia and amines. Polymers of this type are commercial products.

Useful poly(alkyleneimines) c) also include alkyleneimine polymersobtainable by grafting polyvinylamines with at least one alkyleneimine.Preferred are the graft polymers of ethyleneimine. Suitablepolyvinylamines and poly(amidoamines) are mentioned before and in thefollowing.

Suitable poly(alkyleneimines) c) preferably have a number averagemolecular weight in the range of from 150 to 1 000 000, more preferably250 to 10 000.

Further suitable nitrogen containing polymer c) are poly(amidoamines).Poly(amidoamines) in the sense of the invention comprise nitrogen atomsin the form of amide groups and nitrogen atoms in the form of aminegroups. Poly(amidoamines) are obtainable, for example, by condensingpolycarboxylic acids with polyamines.

Suitable polycarboxylic acids for the preparation of poly(amidoamines)are e.g. aliphatic and alicyclic acids. Those aliphatic and alicyclicacids may have e.g. 2 to 30 carbon atoms. Preferred are dicarboxylicacids, for example, oxalic acid, malonic acid, succinic acid, maleicacid, adipic acid, glutaric acid, suberic acid, sebacic acid,heptanedioic acid, octanedioic acid, nonanedioic acid,undecane-am-dicarboxylic acid, dodecane-α,ω-dicarboxylic acid, cis- andtrans-cyclohexane-1,2-dicarboxylic acid, cis and transcyclohexane-1,3-dicarboxylic acid, cis and transcyclohexane-1,4-dicarboxylic acid, cis and transcyclopentane-1,2-dicarboxylic acid, cis and transcyclopentane-1,3-dicarboxylic acid.

In particular, the poly(amidoamines) c) do not contain aromaticdicarboxylic acids, e.g. phthalic acid, isophthalic acid or terephthalicacid.

Suitable tricarboxylic acids or polycarboxylic acids for the preparationof poly(amidoamines) c) are e.g. 1,2,3-propanetricarboxylic acid or1,3,5-cyclohexanetricarboxylic acid.

The carboxylic acids can also be employed for the preparation ofpoly(amidoamines) in the form of derivatives. Such derivatives arepreferably anhydrides, acyl chlorides and esters. In the polycarboxylicacids all or only a part of the acid groups may be derivatised.Preferred esters are esters of C₁-C₈-alcanols, especially the methylester or ethyl ester.

Suitable polyamines for the preparation of poly(amidoamines) contain atleast two primary or secondary nitrogen atoms capable of forming amidegroups. The total number of basic nitrogen atoms in the polyamines ispreferably in the range of from 3 to 100, more preferably 3 to 25, e.g.4 to 10. In the preparation of the poly(amidoamines), it is possible touse mixtures of two or more polycarboxylic acids as well as mixtures oftwo or more polyamines. Examples of suitable polyamines arediethylenetriamine, triethylenetetramine, tetraethylene pentamine,dipropylene triamine, tripropylene tetramine, dihexamethylene triamine,aminopropylethylenediamine and bisaminopropylethylenediamine. Suitablepolyamines are also polyalkylenepolyamines. The polyamines can bepresent in a mixture with diamines. Useful diamines include for example1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane,1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane,isophoronediamine, 4,4′-diaminodiphenyl-methane,1,4-bis(3-aminopropyl)piperazine, 4,9-dioxadodecane-1,12-diamine,4,7,10-trioxatridecane-1,13-diamine or α,ω-diamino compounds ofpolyalkylene oxides.

Lactones or lactams of carboxylic acids having 4 to 8 carbon atoms mayalso be used in the condensation for the preparation ofpoly(amidoamines).

Suitable poly(amidoamines) have at least two terminal amino groups (—NH,—NH₂) or both.

Suitable as poly(amidoamines) are also poly(amidoamines) grafted with atleast one alkyleneimine, e.g. grafted with ethyleneimine. Graftedpoly(amidoamines) are obtainable from the above-describedpoly(amidoamines) by reaction with at least one alkyleneimine in thepresence of Brønsted acids or Lewis acids, such as sulfuric acid orboron trifluoride etherates. The reaction temperature is preferably inthe range of from 80 to 100° C. Compounds of this type are described,for example, in U.S. Pat. No. 4,144,123 and DE-B-24 34 816. The teachingof these documents is incorporated by reference. Suitablepoly(amidoamines) grafted with ethyleneimine have, for example, anaverage molecular weight of from 3000 to 1 000 000 daltons. The graftpolymers generally contain from 10 to 90% by weight of polyamidoaminesas a grafting base and from 90 to 10% by weight of alkyleneimine as agraft.

Suitable poly(amidoamines) c) preferably have a number average molecularweight in the range of from 150 to 1 000 000, more preferably 250 to 10000.

d) Other Starting Materials

In the process of the invention, it is possible to use furthercompounds, e.g. in order to introduce specific end groups into thepolymer or bring about additional crosslinking by means of furtherfunctional groups, to set defined properties or to make furtherreactions on the resulting polymer (polymer-analogous reactions) at alater point in time possible.

Thus, if desired, it is possible to make concomitant use of, forexample, compounds having only one primary amino group (=component d))in order to influence the molecular weight of the polymeric imidazoliumcompounds. The compound having only one primary amino group leads tochain termination and then forms the end group of the polymer chainconcerned. The higher the proportion of compounds having only oneprimary amino group, the lower the molecular weight. Based on 100 mol ofamino compounds having at least two primary amino groups, it ispossible, in a preferred embodiment, to use, for example, from 0 to 10mol of compounds having only one primary group.

e) Protic Acid

The anions of the imidazolium compound are derived from the anions ofthe protic acid(s) employed as component e). It is also possible tosubject the imidazolium compound to an anion exchange. This allows thepreparation of imidazolium compounds with anions for which nocorresponding stable protic acid exists. The anion exchange can beeffected by known methods, e.g. transprotonation, reaction with a metalsalt, ion exchange chromatography, electrolytically or by means of acombination of these measures.

The imidazolium compound employed according to the invention comprisesanions that act as counterions to the imidazolium cations. The anionsare selected from anions of the formula Y^(n−), wherein n is the valencyof the anion. The corresponding protic acid can be represented by theformula Y^(n−)(H⁺)_(n).

In a first embodiment, the anions of the formula Y^(n−) are selectedfrom anions of inorganic acids and low molecular weight organic acid. Inthis embodiment, m is preferably an integer from 1 to 6, more preferablyan integer from 1 to 4, in particularly 1 or 2. In a special embodiment,n is 1.

In a second embodiment, the anions of the formula Y^(n−) are selectedfrom anions of polymeric protic acids, e.g. polyacrylic acid. In thisembodiment, n can assume very high values. Suitable polymeric proticacids comprise at least one ethylenically unsaturated organic acid inpolymerized form. Preferred ethylenically unsaturated organic acid areselected from acrylic acid, methacrylic acid, maleic acid, fumaric acid,itaconic acid, etc. and mixtures thereof. Especially preferred are thehomo- and copolymers of acrylic acid and/or methacrylic acid. Suitablepolymeric protic acids are also the copolymers of at least oneethylenically unsaturated organic acid, preferably selected from acrylicacid methacrylic acid, maleic acid, fumaric acid, itaconic acid with atleast one copolymerizable comonomer, e.g. selected from (meth)acrylates,vinyl esters or aromatic monomers such as styrene and mixtures thereof.

The anions of the imidazolium compound (=anions of the formula Y^(n−))and the anions of the corresponding protic acid (═Y^(n−)(H⁺)_(n)) arepreferably selected from:

the group of halides and halogen-comprising anions of the generalformulae:

F⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻, PF₆ ⁻, AlCl₄ ⁻, Al₂Cl₇—, Al₃Cl₁₀ ⁻, AlBr₄ ⁻,FeCl₄ ⁻, BCl₄ ⁻, SbF₆ ⁻, AsF₆, —ZnCl₃ ⁻, SnCl₃ ⁻, CuCl₂;

the group of pseudohalides and other nitrogen-containing anions of theformulae:

CN⁻, SCN⁻, OCN⁻, NO₂ ⁻, NO₃ ⁻, N(CN)⁻;

the group of sulfates, sulfites and sulfonates of the general formulae:

SO₄ ²⁻, HSO₄ ⁻, SO₃ ²⁻, HSO₃ ⁻, R^(a)OSO₃ ⁻, R²SO₃ ⁻;

the group of phosphates of the general formulae:

PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄ ⁻, R^(a)PO₄ ²⁻, HR^(a)PO₄ ⁻, R^(a)R^(b)PO₄ ⁻;

the group of phosphonates and phosphinates of the general formulae:

R^(a)HPO₃ ⁻, R^(a)R^(b)PO₂ ⁻, R^(a)R^(b)PO₃ ⁻;

the group of phosphites of the general formulae:

PO₃ ³⁻, HPO₃ ²⁻, H₂PO₃ ⁻, R^(a)PO₃ ²⁻, R^(a)HPO₃ ⁻, R^(a)R^(b)PO₃ ⁻;

the group of phosphonites and phosphinites of the general formulae:

R^(a)R^(b)PO₂ ⁻, R^(a)HPO₂ ⁻, R^(a)R^(b)PO⁻, R^(a)HPO⁻;

the group of carboxylates and polybasic carboxylic acids of theformulae:

R^(a)COO⁻; R^(e)(COO⁻)_(f);

the group of borates of the general formulae:

BO₃ ³⁻, HBO₃ ²⁻, H₂BO₃ ⁻, R^(a)R^(b)BO₃ ⁻, R^(a)HBO₃ ⁻, R^(a)BO₃ ²⁻,B(OR^(a))(OR^(b))(OR^(c))(OR^(d))⁻, B(HSO₄)⁻, B(R^(a)SO₄)⁻;

the group of boronates of the general formulae:

R²BO₂ ²⁻, R^(a)R^(b)BO⁻;

the group of halogenated hydrocarbons of the general formulae:

CF₃SO₃, (CF₃SO₃)₂N⁻, CF₃CO₂, CCl₃CO₂ ⁻;

the group of carbonates and carbonic esters of the general formulae:

HCO₃ ⁻, CO₃ ²⁻, R^(a)CO₃ ⁻;

the group of silicates and silicic esters of the general formulae:

SiO₄ ⁴⁻, HSiO₄ ³⁻, H₂SiO₄ ²⁻, H₃SiO₄ ⁻, R^(a)SiO₄ ³⁻, R^(a)R^(b)SiO₄ ²⁻,R^(a)R^(b)R^(c)SiO₄ ⁻, HR^(a)SiO₄ ²⁻, H₂R^(a)SiO₄ ⁻, HR^(a)R^(b)SiO₄ ⁻;

the group of alkylsilane and arylsilane salts of the general formulae:

R^(a)SiO₃ ³⁻, R^(a)R^(b)SiO₂ ²⁻, R^(a)R^(b)R^(c)SiO⁻,R^(a)R^(b)R^(c)SiO₃ ⁻, R^(a)R^(b)R^(c)SiO₂ ⁻, R^(a)R^(b)SiO₃ ²⁻;

the group of carboximides, bis(sulfonyl)imides and sulfonylimides of thegeneral formulae:

the group of methides of the general formula:

the group of alkoxides and aryloxides of the general formula:

R^(a)O⁻;

the group of halometalates of the general formula:

[M_(r)Hal_(t)]^(s−),

where M is a metal and Hal is fluorine, chlorine, bromine or iodine, rand t are positive integers and indicate the stoichiometry of thecomplex and s is a positive integer and indicates the charge on thecomplex;the group of sulfides, hydrogensulfides, polysulfides,hydrogenpolysulfides and thiolates of the general formulae:

S²⁻, HS⁻, [S_(v)]²⁻, [HS_(v)]⁻, [R^(a)S]⁻,

where v is a positive integer from 2 to 10;the group of complex metal ions such as Fe(CN)₆ ³⁻, Fe(CN)₆ ⁴⁻, MnO₄ ⁻,Fe(CO)₄.

In the above formulae, R^(a), R^(b), R^(c) and R^(d) are each,independently of one another, nonacidic hydrogen, C₁-C₃₀-alkyl andaryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-,formyl-, —O—, —CO—, —CO—O— or —CO—N<substituted derivatives thereof, forexample methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl,2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl,2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl,2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl,2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl,4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl,4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl,2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl,2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, phenylmethyl (benzyl), diphenylmethyl,triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl,2-cyclopentylethyl, 3-cyclopentyl-propyl, cyclohexylmethyl,2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl, acetylor C_(q)F_(2(q−a)+(1−b))H_(2a+b) where q≤30, 0≤a≤q and b=0 or 1 (forexample CF₃, C₂F₅, CH₂CH₂—C_((q−2))F_(2(q−2)+1), C₆F₁₃, C₈F₁₇, C₁₀F₂₁,C₁₂F₂₅);

C₃-C₁₂-cycloalkyl and aryl-, heteroaryl-, cycloalkyl-, halogen-,hydroxy-, amino-, carboxy-, formyl-, —O—, —CO— or —CO—O-substitutedderivatives thereof, for example cyclopentyl, 2-methyl-1-cyclopentyl,3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl,3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl orC_(q)F_(2(q−a)−(1−b))H_(2a−b), where q≤30, 0≤a≤q and b=0 or 1;C₂-C₃₀-alkenyl and aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-,amino-, carboxy-, formyl-, —O—, —CO— or —CO—O-substituted derivativesthereof, for example 2-propenyl, 3-butenyl, cis-2-butenyl,trans-2-butenyl or C_(q)F_(2(q−a)−(1−b))H_(2a−b) where q≤30, 0≤a≤q andb=0 or 1;C₃-C₁₂-cycloalkenyl and aryl-, heteroaryl-, cycloalkyl-, halogen-,hydroxy-, amino-, carboxy-, formyl-, —O—, —CO— or —CO—O-substitutedderivatives thereof, for example 3-cyclopentenyl, 2-cyclohexenyl,3-cyclohexenyl, 2,5-cyclohexadienyl or C_(q) F_(2(q−a)−3(1−b))H_(2a−3b)where q≤30, 0≤a≤q and b=0 or 1;aryl or heteroaryl having from 2 to 30 carbon atoms and alkyl-, aryl-,heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-,—O—, —CO— or —CO—O-substituted derivatives thereof, for example phenyl,2-methylphenyl (2-tolyl), 3-methyl-henyl (3-tolyl), 4-methylphenyl,2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl,3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 1-naphthyl,2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl,3-pyridinyl, 4-pyridinyl or C₆F_((5−a))H_(a), where 0≤a≤5; ortwo radicals form an unsaturated, saturated or aromatic ring which mayoptionally be substituted by functional groups, aryl, alkyl, aryloxy,alkyloxy, halogen, heteroatoms and/or heterocycles and may optionally beinterrupted by one or more oxygen and/or sulfur atoms and/or one or moresubstituted or unsubstituted imino groups.

Particular preference is given to R^(a), R^(b), R^(c) and R^(d) eachbeing, independently of one another, hydrogen and particularlypreferably a C₁-C₁₀-alkyl group, preferably a C₁-C₄-alkyl group.

R^(e) (see above formula for the polybasic carboxylic acid) is anorganic radical to which a plurality of carboxylic acid groups arebound. Correspondingly, f is an integer of at least 2. Preferably, f isan integer of 2 to 100 000, more preferably, 2 to 10 000. Such polybasiccarboxylic acids can be, for example, maleic acid or itaconic acid,phthalic acid, isophthalic acid or terephthalic acid; otherpossibilities are polymeric compounds which can be obtained, forexample, by free-radical polymerization of ethylenically unsaturatedcompounds using, possibly among others, monomers having one or twocarboxylic acid groups, e.g. (meth)acrylic acid.

Particular preference is given to carboxylic acids, i.e. protic acids ofthe above carboxylates of the general formulae:

R^(a)COO⁻ and R^(e)(—COO⁻)_(f)

As such carboxylic acids or carboxylates, particular mention may be madeof organic compounds which have from 1 to 20 carbon atoms and compriseone or two carboxylate groups, preferably one carboxylate group.

The carboxylic acids or carboxylates can be aliphatic or aromaticcompounds. Here, aromatic compounds are compounds comprising aromaticgroups. Particular preference is given to aliphatic or aromaticcompounds which, apart from the oxygen atoms of the carboxylate group,comprise no further heteroatoms or at most comprise one or two hydroxylgroups, carbonyl groups or ether groups. Very particular preference isgiven to aliphatic or aromatic compounds which comprise no furtherheteroatoms in addition to the oxygen atoms of the carboxylate group.

As compounds having two carboxylate groups, mention may be made of, forexample, the anions of phthalic acid, of isophthalic acid, ofC₂-C₆-dicarboxylic acids, e.g. oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid.

As compounds having one carboxylate group, mention may be made of theanions of aliphatic, aromatic, saturated or unsaturatedC₁-C₂₀-carboxylic acids, in particular alkanecarboxylic acids,alkenecarboxylic acids, alkynecarboxylic acids, alkadienecarboxylicacids, alkatrienecarboxylic acids, hydroxycarboxylic acids orketonecarboxylic acids or aromatic carboxylic acids such as benzoic acidor phenylacetic acid. Suitable alkanecarboxylic acids, alkenecarboxylicacids and alkadienecarboxylic acids are also known as fatty acids.

As anions Y⁻, mention may be made of, in particular, the anions ofC₁-C₂₀-alkanecarboxylic acids, which may optionally be substituted byone or two hydroxy groups, preferably one hydroxy group.

Further preferred protic acids or preferred anions of protic acids are,apart from carboxylic acids (carboxylates), also sulfonic acid,phosphoric acid or phosphonic acid, with the acid groups of the sulfonicacid, phosphoric acid or phosphonic acid being able to be partiallyesterified.

As phosphoric acid and esters thereof, mention may be made of, inparticular, compounds of the formula VII

where R′ and R″ are each, independently of one another, hydrogen or aC₁-C₁₀-, preferably C₁-C₄-alkyl group.

As phosphonic acid and esters thereof, mention may be made of, inparticular, compounds of the formula VIII

where R′ and R″ are each, independently of one another, hydrogen or aC₁-C₁₀-, preferably C₁-C₄-alkyl group.

Preferably, the at least one protic acid e) is not a hydrohalic acid,especially if the composition is a cosmetic or a personal carecomposition. Accordingly, the imidazolium compound employed in thebiocide composition according to the invention does essentially notcomprise anions of a hydrohalic acid (F⁻, Cl⁻, Br⁻ and I⁻). In thecontext of the invention, an imidazolium compound which does essentiallynot comprise anions of a hydrohalic acid denotes an imidazolium compoundthat comprises at the most 1 mole %, preferably at the most 0.1 mole %,more preferably at the most 0.01 mole, in particular at the most 0.001mole %, based on the total anion content anions of a hydrohalic acid.

Preferably, the anions are selected from:

-   -   the group of carboxylates and polybasic carboxylic acids    -   the group of sulfates, sulfites and sulfonates,    -   the group of phosphates, and    -   the group of halogenated hydrocarbons.

In particular, the anions are selected from formate, acetate,propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate,glycolate (hydroxyacetate), adipate, succinate, phthalate,terephthalate, methoxyacetate, (C₁-C₄-alcoxy)(CH₂CH₂O)_(x)CH₂COO⁻ with xbeing 1-4, benzoate, hydrogenphosphate, sulfate, hydrogensulfate andmethanesulfonate.

In case that the composition is a plant protection composition,especially a fungicidal composition, the anions of the at least oneprotic acid e) and/or the anions of the imidazolium compound canadditionally be selected from chloride, bromide and iodide.

In a preferred embodiment, the biocide composition according to theinvention comprises an imidazolium compound which consists essentiallyof repeat units of the general formula (IV), as defined in thefollowing. Irrespective of the method of their preparation, imidazoliumcompound which consists essentially of repeat units of the generalformula (IV), are particularly advantageous as biocides. Therefore, in afurther aspect the invention provides a biocide composition, comprisingat least one polymeric, ionic compound comprising imidazolium groups(imidazolium compound), which consists essentially of repeat units ofthe general formula (IV)

wherein

-   R¹ and R² are independently selected from hydrogen and in each case    unsubstituted or substituted alkyl (preferably C₁-C₂₀-alkyl), alkoxy    (preferably C₁-C₂₀-alkoxy), alkylthio (preferably C₁-C₂₀-alkylthio),    cycloalkyl (preferably C₃-C₈-cycloalkyl), cycloalkoxy (preferably    C₃-C₈-cycloalkoxy), cycloalkylthio (preferably    C₃-C₈-cycloalkylthio), aryl, aryloxy, arylthio,-   R³ is selected from hydrogen, alkyl (preferably C₁-C₂₀-alkyl),    cycloalkyl (preferably C₃-C₈-cycloalkyl), optionally substituted    aryl and a group —CH₂O—CH₂CH₂_(x)—OR^(a), wherein x is 1, 2, 3, 4,    5 or 6 and R^(a) is hydrogen or C₁-C₄-alkyl,-   each A is independently has one of the general or preferred meanings    given above and does not contain 1,4-bound phenylene units and is    not 2-hydroxy-propane-1,3-diyl or    2-hydroxy-2-methyl-propane-1,3-diyl; and is preferably selected from    a C₁-C₃₀-alkylene group which may be interrupted by one or more    nonadjacent groups which are selected from —O—, —S— and —N(R^(b))—,    where R^(b) is selected from hydrogen, C₁-C₂₀-alkyl and a group    CH₂CH₂—O_(y)—R^(c) wherein y is 1, 2, 3, 4, 5 or 6 and R^(c) is    hydrogen or C₁-C₄-alkyl, preferably O; and is more preferably    selected from a group —(CH₂)_(m)— wherein m is an integer of 3 to    20, preferably 4 to 20, more preferably 4 to 12, where one CH₂ group    may be substituted by a carboxyl or carboxylate group, especially    1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene and    1,12-dodecylene; a group —B—X_(k)—B— in which each X independently    is —O—, —S— or —N(R^(b))—, where R^(b) is selected from hydrogen,    C₁-C₂₀-alkyl and a group CH₂CH₂—O_(y)—R^(c), wherein y is 1, 2, 3,    4, 5 or 6 and R^(c) is hydrogen or C₁-C₄-alkyl, preferably O, each B    independently is C₂-C₆-alkylene, preferably C₂-C₃-alkylene; and k is    an integer from 1 to 100, preferably 1 to 10 and more preferably 2    to 4, especially —[CH₂CH₂O]_(x)—CH₂CH₂— with x being 2 or 3,    preferably 2, and —CH₂CH₂CH₂—[CH₂CH₂O]_(x)—CH₂CH₂CH₂— with x being 2    or 3, preferably 2; and a group of one of the following formulae

-   -   where # is the attachment point to the imidazolium ring; and

-   Y^(n−) is an n-valent anion.

The polymeric, ionic compound preferably contains at least 8 repeatingunits IV, e.g. 8 to 500, preferably 8 to 300, more preferably 8 to 200,even more preferably 8 to 150 and in particular 10 to 150 repeatingunits IV.

In the imidazolium compounds the repeat units of the formula (IV) mayhave the same or different meanings. Thus, it is e.g. possible to employa mixture of different amino compounds c) for the preparation ofimidazolium compounds to obtain repeat units with different groups A. Itis also possible that the imidazolium compounds comprise differentanions Y^(n−).

In the context of the invention, an imidazolium compound which consistsessentially of repeat units of the general formula (IV) denotes animidazolium compound that comprises least 60% by weight, preferably atleast 70% by weight, more preferably at least 80% by weight, inparticularly at least 90% by weight, especially at least 95% by weight,of structural units of the formula IV.

With regard to suitable and preferred meanings of R¹, R², R³, A andY^(n−) reference is made to the afore-mentioned definitions of thosegroups.

In the structural units of the formula IV preferably R¹ and R² arehydrogen.

In the structural units of the formula IV specifically R³ is hydrogen,C₁-C₂₀-alkyl or phenyl and more specifically hydrogen.

In a specific embodiment, in the structural units of the formula IVpreferably A is selected from 1,4-butylene, 1,5-pentylene, 1,6-hexylene,1,8-octylene, 1,12-dodecylene, 3,6-dioxa-1,8-octylene,4,7,10-trioxa-1,13-tridecylene, a group B—X_(k)—B— in which each Xindependently is —O—, —S— or —N(R^(b))—, where R^(b) is selected fromhydrogen, C₁-C₂₀-alkyl and a group CH₂CH₂—O_(y)—R^(c), wherein y is 1,2, 3, 4, 5 or 6 and R^(c) is hydrogen or C₁-C₄-alkyl; preferably O, eachB independently is C₂-C₆-alkylene, preferably C₂-C₃-alkylene; and k isan integer from 1 to 100, preferably 1 to 10 and more preferably 2 to 4;and a group of one of the following formulae

and mixtures thereof.

In a further preferred embodiment, the imidazolium compound comprisesrepeat units of the formula (IV), wherein A is derived from a mixture ofamino compounds by formal elimination of the primary amino groups,comprising at least one amine with two primary amino groups and at leastamine with more than two, in particular three, primary amino groups.

In the structural units of the formula IV preferably the anions Y^(n−)are selected from formate, acetate, propionate, butyrate, pentanoate,hexanoate, heptanoate, octanoate, glycolate (hydroxyacetate), adipate,succinate, phthalate, terephthalate, (C₁-C₄-alcoxy)(CH₂CH₂O)_(x)CH₂COO⁻with x being 1-4, benzoate, sulfate, hydrogensulfate, methanesulfonate.

The polymeric ionic compound comprosing imidazolium groups preferablyhas a weight average molecular weight M_(w) (determined according to themethods described in the examples) of from 300 bis 500000, morepreferably of from 500 to 300000, even more preferably of from 1000 to200000, in particular 2000 to 200000 and specifically 4000 to 200000.The dispersity PDI (M_(w)/M_(n); M_(n)=number-average molecular weight)is preferably in the range from 1.1 to 20, more preferably from 1.5 to15.

The biocide composition according to the invention can be employedagainst a wide variety of harmful organisms, in particularmicroorganisms, especially bacteria, fungi (including inter alia yeasts,slime molds (myxomycetes) and water molds (oomycetes) and the spores ofthe fungi), algae, viruses and mycoplasma. Examples of gram-positivebacteria are Micrococcaceae, Streptococcaceae, Bacilli,Lactobacillaceae, Actinomycetales, especially Mycobacterium,Dermatophilus, Nocardiaceae, Streptomyces and Corynebacterium. Examplesof gram-negative microorganisms are Spirochaetales (e.g. Spirochaetaceaeand Leptospiraceae), Pseudomonadaceae, Legionellaceae, Neisseriaceae,Enterobacteriaceae, Vibrionaceae, Pasteurellaceae, Bacteroidaceae,Veillonellaceae, Rickettsiaceae, Bartonellaceae and Chlamydiaceae, aswell as Brucellaceae.

Examples of yeasts include the families Cryptococcaceae andSporobolomycetaceae, in which are found human pathogenic kinds ofCandida, Trichospores as well as Cryptococcus neoformans. Examples ofthese are Candida albicans and Saccharomyces cerevisiae.

An example of a mold within the family zygomycetes is Mucorales;examples of the family Hypomycetes are Aspergillus and Penicillium andan example of the family Bodariales is Neurospora. The representativesof molds most mentioned are, for example, Alternaria alternata,Aspergillus niger and Penicillium funiculosum.

Examples of algae include Scenedesmus obliquus, Euglena gracillis,Chlorella pyrenoidosa, Chlamydomonas pulsatilla, Chlorella salina,Phaeodactylum tricornutum, Chlorella sp, Pleurococcus sp, Nostocmuscorum, Oscillatoria tenuis, Stichococcus bacillaris and Trentepohliaaurea.

Mycoplasma denotes a special genus of bacteria that lack a cell wall.Examples are M. pneumoniae and M. genitalium.

In a special embodiment, the biocide composition according to theinvention is employed against Staphylococcus aureus and Pseudomonasaeruginosa.

The ionic compounds comprising imidazolium groups (=imidazoliumcompounds) are in the following also denoted as component A).

The content of the imidazolium compounds in the biocide compositions ofthe invention can be varied over wide ranges. Preferably, the biocidecomposition comprises the at least one imidazolium compound in an amountof from 0.01 to 100 wt-%, more preferably 0.1 to 99.9 wt-%, inparticular 0.5 to 95 wt-%, based on the total weight of the composition.Especially, the biocide composition comprises the at least oneimidazolium compound in an amount of from 0.01 to 10 wt-%, moreespecially 0.05 to 5 wt-%, in particular 0.1 to 1 wt-%, based on thetotal weight of the composition.

In addition to at least one imidazolium compound (component A), thebiocide compositions of the invention may comprise at least one furthermicrobicidal compound different from the compounds of component (A)(=component B).

Suitable further microbicidal compounds (B) are selected from alcohols,including halogenated alcohols,

-   -   isothiazolones,    -   activated halogen compounds,    -   formaldehyde release compounds,    -   phenolic compounds,    -   aldehydes,    -   acids and esters,    -   biphenyls,    -   urea derivatives,    -   O-acetals, O-formals,    -   N-acetals, N-formals,    -   benzamidines,    -   phthalimides,    -   pyridine derivatives,    -   quaternary ammonium and phosphonium compounds,    -   amines,    -   amphoteric compounds,    -   dithiocarbamates,    -   compounds containing active oxygen such as peroxide,    -   inorganic salts such as metal oxides, metal chlorides, metal        sulfates, etc.,    -   organic metal salts, such as Zn-pyrithion, Ag-lactate, etc.,    -   mixtures thereof.

Examples of alcohol compounds which may serve as the microbiocidallyeffective component (B) are 2-bromo-2-nitropropane-1,3-diol and2-(hydroxymethyl)-2-nitro-1,3-propanediol. Examples of isothiazolonecompounds are 5-chloro-2-methyl-2H-isothiazol-3-one (CIT),2-methyl-2H-isothiazol-3-one (MIT), 1,2-benzisothiazol-3(2H)-one,2-n-octyl-2H-isothiazol-3-one, 4,5-dichloro-2-octyl-2H-isothiazol-3-oneand 2-butyl-benzo-[d]isothiazol-3-one and mixtures thereof with oneanother, including a mixture of CIT with MIT or mixtures of CIT or MITwith any of 1,2-benzoisothiazol-3(2H)-one, 2-octyl-2H-isothiazol-3-one,4,5-dichloro-2-octyl-2H-isothiazol-3-one and2-butyl-benzo[d]isothiazol-3-one. Examples of other compounds aredibromodicyanobutane, [beta]-bromo-[beta]-nitrostyrene,7a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c]oxazole,tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)-imidazo[4,5-d]-imidazole-2,5(1H,3H)-dione,1,3-dimethyl-5,5-dimethylhydantoin, diazolidinyl ureas andimidazolidinyl ureas, N′-(3,4-dichlorophenyl)-N,N-dimethyl urea,3,3′-methylenebis(5-methyl-oxazolidine), 2-sodiumsulfidopyridine-N-oxideand its metal salts, dibromonitritopropionamide,tetrakishydroxymethylphosphonium salts, ortho-phenylphenol and salts ofortho-phenylphenol, 1-(3-chloroallyl)-3,5,7-triaza-1-azodiadamantanesalts, (5-chloro-2,4-dichlorophenoxy)phenol, 3,4,4′-trichlorocarbanilide(triclocarban), o-benzo-p-chlorophenol, p-hydroxybenzoates,2-(thiocyanomethylthio) benzothiazole,3,5-dimethyl-1,3,5-thiadiazinane-2-thione, 2,4-dichlorobenzyl alcohol,chlorothalonil, methylenebis(thiocyanate), peracetic acid,4,4-dimethyl-oxazolidine, phenoxyethanol, phenoxypropanol,2,6-dimethyl-m-dioxan-4-ol-acetate, glutaraldehyde, glyoxal,ortho-phthalaldehyde, 4-(2-nitrobutyl)-morpholine, triazines such as1,3,5-tris-(2-hydroxyethyl)-1,3,5-hexahydrotriazine, quaternary ammoniumcompounds such as benzalkoniumchloride, polyhexamethylenebiguanidesalts, poly(oxyethylene(dimethylimino)ethylene(dimethylimino)-ethylenedichloride, chlorhexidine gluconate, chloroisocyanurates, halogenatedhydantoins such as 1-bromo-3-chloro-5,5-dimethylhydantoin and polaminessuch as polyvinylamine- and polyethylene imine derivatives. Furtherexamples include IPBC, terbutryn, ziram, zineb, dichlofluanid,trichlofuanid, folpet, metal dihexa-2,4-dienoate, tebuconazole,3-benzo(b)thien-2-yl-5,6-dihydro-1,4,2-oxathiazine, 4-oxide,pyrithiones, thiram, cybutryne, MBT, carbendazim, diuron, chlorotoluron,fluorometuron, thiabendazole, metazachlor, CuSCN, or dicopper oxide.

Preferred components (B) are 2-bromo-2-nitropropane-1,3-diol,2-methyl-2H-isothiazol-3-one, 1,2-benzisothiazol-3(2H)-one,2-n-octyl-2H-isothiazol-3-one, a mixture of5-chloro-2-methyl-2H-isothiazol-3-one with 2-methyl-2H-isothiazol-3-one,dibromodicyanobutane,tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)-imidazo[4,5-d]-imidazole-2,5(1H,3H)-dione,3,3′-methylenebis(5-methyl-oxazolidine),1,3-dimethyl-5,5-dimethylhydantoin, tetrakishydroxymethylphosphoniumsalts, ortho-phenylphenol and salts of ortho-phenylphenol,1-(3-chloroallyl)-3,5,7-triaza-1-azodiadamantane salts,(5-chloro-2,4-dichlorophenoxy)phenol, 3,4,4′-trichlorocarbanilide(triclocarban), p-hydroxybenzoates, 2-(thiocyanomethylthio)benzothiazole, 3,5-dimethyl-1,3,5-thiadiazinane-2-thione),iodo-2-propynylbutylcarbamate, 2-sodiumsulfidopyridine-N-oxide and itsmetal salts, 2,4-dichlorobenzyl alcohol, chlorothalonil,methylenebis(thiocyanate), phenoxyethanol, phenoxypropanol, triazinessuch as 1,3,5-tris-(2-hydroxyethyl)-1,3,5-hexahydrotriazine, quaternaryammonium compounds such as benzalkoniumchloride, polyhexamethylenebiguanide salts, poly(oxyethylene(dimethyimino)ethylene(dimethylimino)ethylene dichloride, chlorhexidine gluconate,chloroisocyanurates and polyvinylamines, especially the polyaminesdisclosed in WO-A-97/32477.

If the biocide composition according to the invention comprisescomponents (A) and (B), the amounts of the components (A) and (B) in thecomposition are preferably 1 to 99 wt % of (A) and 99 to 1 wt % of (B),more preferably 10 to 90 wt % of (A) and 90 to 10 wt % of (B),especially 20 to 80 wt % of (A) and 80 to 20 wt % of (B). Preferably,the biocide composition comprises the sum of compounds (A) and (B) in anamount of from 0.01 to 100 wt %, more preferably 0.1 to 99.9 wt %, inparticular 0.5 to 95 wt %, based on the total weight of the composition.Especially, the biocide composition comprises the sum of compounds (A)and (B) in an amount of from 0.01 to 10 wt %, more especially 0.05 to 5wt-%, in particular 0.1 to 1 wt-%, based on the total weight of thecomposition.

The biocide composition according to the invention, comprising acomponent (A), optionally (B) and optionally further components can bemade up into the usual formulations and preparations that are suitablefor the desired purpose. The biocide composition according to theinvention can be provided and/or applied as a solid or as a liquid. Thisencompasses compositions in form of aerosols. The biocide compositionaccording to the invention can be formulated e.g. as powder, granulate,pellets, pills, agglomerates, solutions, emulsions, suspensions,dispersions, pastes, in combination with carrier materials, etc.

The biocide compositions according to the invention can be formulatedfree from solvent or with a suitable solvent. Generally, the imidazoliumcompounds used according to the invention are soluble in most proticsolvents, swellable in most aprotic polar solvents and insoluble in mostnonpolar solvents. Suitable solvents for the biocide compositionsaccording to the invention are selected from among water, alcohols, suchas methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol,diols and polyols, such as ethanediol and propanediol, amino alcohols,such as ethanolamine, diethanolamine and triethanolamine, ethers, e.g.tetrahydrofuran, diethyl ether, methyl tert-butyl ether and diethyleneglycol monomethyl ether, ketones, such as acetone and methyl ethylketone, esters, e.g. ethyl acetate, formamide, dimethylformamide (DMF),dimethylacetamide, dimethyl sulfoxide (DMSO), acetonitrile, aromaticsolvents, e.g. benzene, toluene, ethylbenzene or xylenes, halogenatedsolvents, e.g. dichloromethane, chloroform, carbon tetrachloride,dichloroethane or chlorobenzene, aliphatic solvents, e.g. pentane,hexane, heptane, octane, ligroin, petroleum ether, cyclohexane anddecalin, and mixtures thereof.

The solvent is preferably selected from among water, water-miscibleorganic solvents and mixtures thereof. The solvent is particularlypreferably selected from among water, methanol, ethanol, n-propanol,isopropanol, n-butanol, tert-butanol and mixtures thereof.

A multitude of different active substances and additives can beformulated in the biocide compositions according to the invention.

Fungicidal Composition

In another aspect, the invention relates to a fungicidal compositionatleast one polymeric, ionic compound comprising imidazolium groups(imidazolium compound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal.

Preferably, the amino compound having at least two primary amino groupsis not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane; and/or the polymer comprises atleast 8, preferably at least 10 imidazolium rings; and/or the main chainof the at least one compound comprising imidazolium groups does notcontain 1,4-bound phenylene rings and/or the main chain of the at leastone imidazolium compound apart from the nitrogen atoms of theimidazolium groups does not contain any quaternary nitrogen atoms thatbear 4 residues that are different from hydrogen.

In one preferred embodiment, the amino compound having at least twoprimary amino groups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane.

In another embodiment, the polymer comprises at least 8, preferably atleast 10 imidazolium rings.

In another embodiment, the main chain of the at least one compoundcomprising imidazolium groups does not contain 1,4-bound phenylene rings

In another embodiment, the main chain of the at least one imidazoliumcompound apart from the nitrogen atoms of the imidazolium groups doesnot contain any quaternary nitrogen atoms that bear 4 residues that aredifferent from hydrogen.

In one preferred embodiment, the amino compound having at least twoprimary amino groups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane and the polymer comprises atleast 8, preferably at least 10 imidazolium rings.

In particular, the polymer has one of the general or preferred meaningsgiven above in context with the biocidal composition, and the fungicidalcomposition has one of the general or preferred meanings given above forthe biocidal composition; i.e. the above-described biocidal compositionis preferably a fungicidal composition.

In a particular embodiment, the composition contains at least onefurther agrochemically active compound V, e.g. at least one herbicide,insecticide, growth regulator, fungicide (different of course from theimidazolium compound) or fertilizer.

The fungicidal composition containing the polymeric, ionic compoundcontaining imidazolium rings and at least one further agrochemicallyactive compound V may be a physical mixture of these components.Accordingly, the invention also provides a mixture comprising thesecomponents. However, the composition may also be any combination ofthese components, it not being required for the polymeric, ioniccompound and compound V to be present together in the same formulation.

An example of a composition according to the invention or to be usedaccording to the invention in which the at least one polymeric, ioniccompound and the at least one compound V are not present together in thesame formulation is a combipack. In a combipack, two or more componentsof a combipack are packaged separately, i.e., not jointlypre-formulated. As such, combipacks include one or more separatecontainers such as vials, cans, bottles, pouches, bags or canisters,each container containing a separate component for an agrochemicalcomposition. One example is a two-component combipack. Accordingly thepresent invention also relates to a two-component combipack, comprisinga first component which in turn comprises at least one compoundpolymeric, ionic compound, a liquid or solid carrier and, ifappropriate, at least one surfactant and/or at least one customaryauxiliary, and a second component which in turn comprises at least onecompound V, a liquid or solid carrier and, if appropriate, at least onesurfactant and/or at least one customary auxiliary. More details, e.g.as to suitable liquid and solid carriers, surfactants and customaryauxiliaries are described below.

Practical agricultural experience has shown that the repeated andexclusive application of an individual active compound in the control ofharmful fungi leads in many cases to a rapid selection of those fungusstrains which have developed natural or adapted resistance against theactive compound in question. Effective control of these fungi with theactive compound in question is then no longer possible. To reduce therisk of the selection of resistant fungus strains, mixtures of differentactive compounds are nowadays conventionally employed for controllingharmful fungi. By combining active compounds having different mechanismsof action, it is possible to ensure successful control over a relativelylong period of time.

Using the polymeric, ionic compound comprising imidazolium groups incombination with at least one agrochemically active compound V resultsin many cases in an expansion of the fungicidal spectrum of activitybeing obtained or in a prevention of fungicide resistance development.Furthermore, in many cases, synergistic effects are obtained.

The following list of active compounds V, in conjunction with which thepolymeric, ionic compounds according to the invention comprisingimidazolium groups can be used, is intended to illustrate the possiblecombinations but does not limit them:

-   A) Respiration Inhibitors    -   Inhibitors of complex III at Q_(o) site (e.g. strobilurins):        azoxystrobin, coumethoxy¬strobin, coumoxystrobin, dimoxystrobin,        enestroburin, fenaminstrobin, fenoxy¬strobin/flufenoxystrobin,        fluoxastro¬bin, kresoxim-methyl, meto¬minostrobin, orysastrobin,        picoxy¬strobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,        trifloxystrobin,        2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid        methyl ester and 2        (2-(3-(2,6-di¬chlorophenyl)-1-methyl-allylidene¬aminooxy¬methyl)-phenyl)-2-methoxyimino-N        methyl-acetamide, pyribencarb, triclopyricarb/chlorodin¬carb,        famoxadone, fenamidone;    -   inhibitors of complex III at Q_(i) site: cyazofamid, amisulbrom,        [(3S,6S,7R,8R)-8-benz¬yl-3-[(3-acetoxy-4        methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-di¬oxonan-7-yl]2        methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet¬oxymeth¬oxy)-4-methoxy-pyridine-2        carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2        methylpropanoate,        [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobut¬oxycarbonyloxy-4-meth¬oxy-pyri¬dine-2        carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]        2-methylpro¬panoate,        [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-ben¬zodioxol-5-ylmethoxy)-4-methoxy-pyri¬dine-2-car¬bonyl]amino]-6-methyl-4,9-di¬oxo-1,5-dioxonan-7-yl]2-methyl¬propanoate;        (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6        methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl        2-methylpropanoate    -   inhibitors of complex II (e.g. carboxamides): benodanil,        bixafen, boscalid, carboxin, fen¬furam, fluopyram, flutolanil,        fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin,        penflufen, penthiopyrad, sedaxane, tecloftalam, thifluz¬amide,        N-(4′-trifluoromethylthiobiphenyl-2-yl)-3        difluoromethyl-1-methyl-1H pyr¬azole-4-carboxamide,        N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5        fluoro-1H-pyrazole-4 carboxamide,        N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-me¬thanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,        3        (difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3        (trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3-(trifluorometh¬yl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        3-(difluoro¬methyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,        1,3,5-tri¬methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide;    -   other respiration inhibitors (e.g. complex I, uncouplers):        diflumetorim,        (5,8-difluoro¬quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine;        nitrophenyl derivates: binapacryl, dinobuton, dinocap,        fluazinam; ferimzone; organometal compounds: fentin salts, such        as fentin-acetate, fentin chloride or fentin hydroxide;        ametoctradin; and silthiofam;-   B) Sterol Biosynthesis Inhibitors (SBI Fungicides)    -   C14 demethylase inhibitors (DMI fungicides): triazoles:        azaconazole, bitertanol, bromuconazole, cyproconazole,        difenoconazole, diniconazole, diniconazole-M, epoxiconazole,        fenbuconazole, fluquinconazole, flusilazole, flutriafol,        hexaconazole, imibenconazole, ipconazole, metconazole,        myclobutanil, oxpoconazole, paclobutrazole, penconazole,        propiconazole, prothio¬conazole, simeconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triticonazole,        uniconazole,        1-[rel-(2S;3R)-3-(2-chloro¬phenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5        thio¬cyanato-1H-[1,2,4]triazole,        2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl¬methyl]-2H        [1,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate,        prochloraz, triflumizol; pyrimidines, pyridines and piperazines:        fenarimol, nuarimol, pyrifenox, triforine;    -   Delta14-reductase inhibitors: aldimorph, dodemorph,        dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin,        piperalin, spiroxamine;    -   Inhibitors of 3-keto reductase: fenhexamid;-   C) Nucleic Acid Synthesis Inhibitors    -   phenylamides or acyl amino acid fungicides: benalaxyl,        benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam),        ofurace, oxadixyl;    -   others: hymexazole, octhilinone, oxolinic acid, bupirimate,        5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine,        5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4 amine;-   D) Inhibitors of Cell Division and Cytoskeleton    -   tubulin inhibitors, such as benzimidazoles, thiophanates:        benomyl, carbendazim, fuberidazole, thiabendazole,        thiophanate-methyl; triazolopyrimidines: 5-chloro-7 (4        methyl¬piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri¬azolo[1,5        a]pyrimidine    -   other cell division inhibitors: diethofencarb, ethaboxam,        pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;-   E) Inhibitors of Amino Acid and Protein Synthesis    -   methionine synthesis inhibitors (anilino-pyrimidines):        cyprodinil, mepanipyrim, pyrimethanil;    -   protein synthesis inhibitors: blasticidin-S, kasugamycin,        kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin,        oxytetracyclin, polyoxine, validamycin A;-   F) Signal Transduction Inhibitors    -   MAP/histidine kinase inhibitors: fluoroimid, iprodione,        procymidone, vinclozolin, fenpiclonil, fludioxonil;    -   G protein inhibitors: quinoxyfen;-   G) Lipid and Membrane Synthesis Inhibitors    -   Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos,        pyrazophos, isoprothiolane;    -   lipid peroxidation: dicloran, quintozene, tecnazene,        tolclofos-methyl, biphenyl, chloroneb, etridiazole;    -   phospholipid biosynthesis and cell wall deposition:        dimethomorph, flumorph, mandipropamid, pyrimorph,        benthiavalicarb, iprovalicarb, valifenalate and        N-(1-(1-(4-cyano-phenyl)¬ethanesulfonyl)-but-2-yl) carbamic        acid-(4-fluorophenyl) ester;    -   compounds affecting cell membrane permeability and fatty acides:        propamocarb, propamo¬carb-hydrochlorid    -   fatty acid amide hydrolase inhibitors:        1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3        isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1        yl]ethanone-   H) Inhibitors with Multi Site Action    -   inorganic active substances: Bordeaux mixture, copper acetate,        copper hydroxide, copper oxychloride, basic copper sulfate,        sulfur;    -   thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,        metiram, propineb, thiram, zineb, ziram;    -   organochlorine compounds (e.g. phthalimides, sulfamides,        chloronitriles): anilazine, chlorothalonil, captafol, captan,        folpet, dichlofluanid, dichlorophen, flusulfamide,        hexachlorobenzene, pentachlorphenole and its salts, phthalide,        tolylfluanid,        N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;    -   guanidines and others: guanidine, dodine, dodine free base,        guazatine, guazatine-acetate, iminoctadine,        iminoctadine-triacetate, iminoctadine-tris(albesilate),        dithianon,        2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone;-   I) Cell Wall Synthesis Inhibitors    -   inhibitors of glucan synthesis: validamycin, polyoxin B; melanin        synthesis inhibitors: pyroquilon, tricyclazole, carpropamid,        dicyclomet, fenoxanil;-   J) Plant Defence Inducers    -   acibenzolar-S-methyl, probenazole, isotianil, tiadinil,        prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum,        phosphorous acid and its salts;-   K) Unknown Mode of Action    -   bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet,        debacarb, diclo¬mezine, difenzoquat, difenzoquat-methylsulfate,        diphenylamin, fenpyrazamine, flumetover, flusulfamide,        flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl,        oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide,        2-butoxy-6-iodo-3 propylchromen-4-one,        N-(cyclo¬propylmethoxyimino-(6-difluoro-methoxy-2,3        di¬fluoro-phenyl)-methyl)-2-phenyl acetamide,        N′-(4-(4-chloro-3-trifluoromethyl-phen¬oxy)-2,5-dimethyl-phenyl)-N-ethyl-N        methyl formamidine,        N′(4-(4-fluoro-3-trifluoro¬methyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(2-methyl-5-trifluoromethyl-4-(3-trimethyl¬silanyl-prop¬oxy)-phenyl)-N-ethyl-N-methyl        forma¬midine, N′-(5-difluoromethyl-2        methyl-4-(3-tri¬methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine,        2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4        carboxylic acid methyl-(1,2,3,4-tetrahydro-naphthalen-1        yl)-amide,        2-{1-[2-(5-meth¬yl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic        acid methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-amide,    -   1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-    -   2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,        methoxy-acetic acid    -   6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester,        N-Methyl-2-{1-[(5-methyl-3-tri¬fluoro¬methyl-1H-pyr¬azol-1-yl)-acetyl]-piperi¬din-4-yl}-N-[(1R)-1,2,3,4-tetrahydro¬naphthalen-1-yl]-4-thi¬azolecarboxamide,        3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine,        3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine        (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)        cyclopropane¬carboxylic acid amide, 5-chloro-1        (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-ben¬zoimidazole,    -   2-(4-chloro-phenyl)-N-[4-(3,4-dimeth¬oxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;-   L) Antifungal biocontrol agents, plant bioactivators: Ampelomyces    quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany),    Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH),    Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH,    Germany), Bacillus pumilus (e.g. NRRL Accession No. B 30087 in    SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus    subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX    and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var.    amylolique¬faciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals,    Inc., USA), Candida oleophila 1-82 (e.g. ASPIRE® from Ecogen Inc.,    USA), Candida saitoana (e.g. BIOCURE® (in mixture with lysozyme) and    BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan    (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f.    catenulata, also named Gliocladium catenulatum (e.g. isolate J1446:    PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g.    CONTANS® from Prophyta, Germany), Cryphonectria parasitica (e.g.    Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g.    YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium    oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from    Natural Plant Protection, France), Metschnikowia fructicola (e.g.    SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT®    from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from    Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX® from Plant    Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g.    POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria    sachlinensis (e.g. REGALIA® from Marrone Biolnnovations, USA),    Talaromyces flavus V117b (e.g. PROTUS® from Prophyta, Germany),    Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical    Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from    Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g. PLANTSHIELD®    der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO®    from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and    TRICHODERMA 20000 from Mycontrol Ltd., Israel and Makhteshim Ltd.,    Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm    Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080    (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T.    harzianum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T.    stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens    GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO®    from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T.    Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from    Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN®    from Botry-Zen Ltd, NZ);-   M) Growth Regulators    -   abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,        brassinolide, butralin, chlormequat (chlormequat chloride),        choline chloride, cyclanilide, daminozide, dike¬gulac,        dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin,        flurprimidol, fluthi¬acet, forchlorfenuron, gibberellic acid,        inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide,        mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6        benzyladenine, paclobutrazol, prohexadione        (prohexadione-calcium), prohydrojasmon, thidiazuron,        triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri        iodobenzoic acid, trinexapac-ethyl and uniconazole;-   N) Herbicides    -   acetamides: acetochlor, alachlor, butachlor, dimethachlor,        dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor,        napropamide, naproanilide, pethoxamid, pretilachlor, propachlor,        thenylchlor;    -   amino acid derivatives: bilanafos, glyphosate, glufosinate,        sulfosate;    -   aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl,        fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop,        quizalofop, quizalofop-P-tefuryl;    -   Bipyridyls: diquat, paraquat;    -   (thio)carbamates: asulam, butylate, carbetamide, desmedipham,        dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb,        phenmedipham, prosulfocarb, pyributicarb, thiobencarb,        triallate;    -   cyclohexanediones: butroxydim, clethodim, cycloxydim,        profoxydim, sethoxydim, tepraloxydim, tralkoxydim;    -   dinitroanilines: benfluralin, ethalfluralin, oryzalin,        pendimethalin, prodiamine, trifluralin;    -   diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop,        ethoxyfen, fomesafen, lactofen, oxyfluorfen;    -   hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;    -   imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr,        imazaquin, imazethapyr;    -   phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid        (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB,        Mecoprop;    -   pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet,        norflurazon, pyridate;    -   pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr,        fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;    -   sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron,        chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron,        ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron,        foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron,        mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron,        oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,        rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron,        triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron,        tritosulfuron, 1        ((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;    -   triazines: ametryn, atrazine, cyanazine, dimethametryn,        ethiozin, hexazinone, metamitron, metribuzin, prometryn,        simazine, terbuthylazine, terbutryn, triaziflam;    -   ureas: chlorotoluron, daimuron, diuron, fluometuron,        isoproturon, linuron, metha¬benzthiazuron, tebuthiuron;    -   other acetolactate synthase inhibitors: bispyribac-sodium,        cloransulam-methyl, diclosulam, florasulam, flucarbazone,        flumetsulam, metosulam, ortho-sulfamuron, penoxsulam,        propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid,        pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone,        pyroxsulam;    -   others: amicarbazone, aminotriazole, anilofos, beflubutamid,        benazolin, bencarbazone, benfluresate, benzofenap, bentazone,        benzobicyclon, bicyclopyrone, bromacil, bromobutide,        butafenacil, butamifos, cafenstrole, carfentrazone,        cinidon-ethyl, chlorthal, cinmethylin, clomazone, cumyluron,        cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera        monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone,        fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam,        flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole,        lenacil, propanil, propyzamide, quinclorac, quinmerac,        mesotrione, methyl arsonic acid, naptalam, oxadiargyl,        oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil,        pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate,        quinoclamine, saflufenacil, sulcotrione, sulfentrazone,        terbacil, tefuryltrione, tembotrione, thiencarbazone,        topramezone,        (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic        acid ethyl ester,        6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid        methyl ester,        6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,        4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic        acid,        4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic        acid methyl ester, and        4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic        acid methyl ester.-   O) Insecticides    -   organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,        chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,        dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,        fenitrothion, fenthion, isoxathion, malathion, methamidophos,        methidathion, methyl-parathion, mevinphos, monocrotophos,        oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,        phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,        profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,        triazophos, trichlorfon;    -   carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb,        carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,        methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb,        triazamate;    -   pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,        cyphenothrin, cypermethrin, alpha-cypermethrin,        beta-cypermethrin, zeta-cypermethrin, deltamethrin,        esfen¬valerate, etofenprox, fenpropathrin, fenvalerate,        imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,        pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate,        tefluthrin, tetramethrin, tralomethrin, transfluthrin,        profluthrin, dimefluthrin;    -   insect growth regulators: a) chitin synthesis inhibitors:        benzoylureas: chlorfluazuron, cyramazin, diflubenzuron,        flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,        teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,        etox¬azole, clofentazine; b) ecdysone antagonists: halofenozide,        methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:        pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis        inhibitors: spirodiclofen, spiromesifen, spirotetramat;    -   nicotinic receptor agonists/antagonists compounds: clothianidin,        dinotefuran, flupyradifurone, imidacloprid, thiamethoxam,        nitenpyram, acetamiprid, thiacloprid, 1        2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;    -   GABA antagonist compounds: endosulfan, ethiprole, fipronil,        vaniliprole, pyrafluprole, pyriprole,        5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H        pyrazole-3-carbothioic acid amide;    -   macrocyclic lactone insecticides: abamectin, emamectin,        milbemectin, lepimectin, spinosad, spinetoram;    -   mitochondrial electron transport inhibitor (METI) I acaricides:        fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;    -   METI II and III compounds: acequinocyl, fluacyprim,        hydramethylnon;    -   Uncouplers: chlorfenapyr;    -   oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron,        fenbutatin oxide, propargite;    -   moulting disruptor compounds: cryomazine;    -   mixed function oxidase inhibitors: piperonyl butoxide;    -   sodium channel blockers: indoxacarb, metaflumizone;    -   others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,        pymetrozine, sulfur, thiocyclam, flubendiamide,        chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen,        flupyrazofos, cyflumetofen, amidoflumet, imicyafos,        bistrifluron, and pyrifluquinazon.

The compounds V, their preparation and their biological activity e.g.against harmful fungi, pests or weed is known (cf.:http://www.alanwood.net/pesticides/); these substances are commerciallyavailable and known, for example, from the references below:

benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE 29 03612); metalaxyl, methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB15 00 581); ofurace,(RS)-α-(2-chloro-N-2,6-xylylacetamido)-γ-butyrolactone [CAS RN58810-48-3]; oxadixyl;N-(2,6-dimethylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide (GB20 58 059); aldimorph, “4-alkyl-2,5(or 2,6)-dimethylmorpholine”,comprising 65-75% of 2,6-dimethylmorpholine and 25-35% of2,5-dimethylmorpholine, comprising more than 85% of 4-dodecyl-2,5(or2,6)-dimethylmorpholine, where “alkyl” also includes octyl, decyl,tetradecyl and hexadecyl, with a cis/trans ratio of 1:1 [CAS RN91315-15-0]; dodine, 1-dodecylguanidinium acetate (Plant Dis. Rep., Vol.41, p. 1029 (1957)); dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine(DE 1198125); fenpropimorph,(RS)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine(DE 27 52 096); fenpropidin,(RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine (DE 27 52 096);guazatine, mixture of the reaction products from the amidation oftechnical grade iminodi(octa-methylene)diamine, comprising variousguanidines and polyamines [CAS RN 108173-90-6]; iminoctadine,1,1′-iminodi(octamethylene)diguanidine (Congr. Plant Pathol. 1, p. 27(1968); spiroxamine,(8-tert-butyl-1,4-dioxaspiro[4.5]dec-2-yl)diethylamine (EP-A 281 842);tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE 11 64 152);pyrimethanil, 4,6-dimethylpyrimidin-2-ylphenylamine (DD-A 151 404);mepanipyrim, (4-methyl-6-prop-1-ynylpyrimidin-2-yl)phenylamine (EP-A 224339); cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl)phenylamine(EP-A 310 550); cycloheximid,4-{(2R)-2-[(1S,3S,5S)-3,5-dimethyl-2-oxocyclohexyl]-2-hydroxyethyl}piperidine-2,6-dione[CAS RN 66-81-9]; griseofulvin,7-chloro-2′,4,6-trimethoxy-6′-methylspiro[benzo-furan-2(3H),1′-cyclohex-2′-ene]-3,4′-dione[CAS RN 126-07-8]; kasugamycin,3-O-[2-amino-4-[(carboxyiminomethyl)amino]-2,3,4,6-tetradeoxy-α-D-arabino-hexopyranosyl]-D-chiro-inositol[CAS RN 6980-18-3]; natamycin,(8E,14E,16E,18E,20E)-(1R,3S,5R,7R,12R,22R,24S,25R,26S)-22-(3-amino-3,6-dideoxy-β-D-mannopyranosyloxy)-1,3,26-trihydroxy-12-methyl-10-oxo-6,11,28-trioxatricyclo[22.3.1.05,7]octacosa-8,14,16,18,20-pentaene-25-carboxylicacid [CAS RN 7681-93-8]; polyoxin,5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1-(5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl)-1,5-dideoxy-β-D-allofuranuronicacid [CAS RN 22976-86-9]; streptomycin,1,1′-{1-L-(1,3,5/2,4,6)-4-[5-deoxy-2-O-(2-deoxy-2-methylamino-α-L-glucopyranosyl)-3-C-formyl-α-L-lyxofuranosyloxy]-2,5,6-trihydroxycyclohex-1,3-ylene}diguanidine(J. Am. Chem. Soc. 69, p. 1234 (1947)); bitertanol,β-([1,1′-biphenyl]-4-yloxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(DE 23 24 020); bromuconazole,1-[[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furanyl]methyl]-1H-1,2,4-triazole(Proc. Br. Crop. Prot. Conf. 1990—Pests Dis. Vol. 1, p. 459);cyproconazole,2-(4-chlorophenyl)-3-cyclopropyl-1-[1,2,4]triazol-1-ylbutan-2-ol (U.S.Pat. No. 4,664,696); difenoconazole,1-{2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-[1,3]dioxolan-2-ylmethyl}-1H-[1,2,4]triazole(GB-A 2 098 607); diniconazole,(βE)-β-[(2,4-dichlorophenyl)methylene]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(Noyaku Kagaku, 1983, Vol. 8, p. 575); enilconazole (imazalil),1-[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole (Fruits28, p. 545, 1973); epoxiconazole,(2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,2,4-triazole(EP-A 196 038); fenbuconazole,α-[2-(4-chloro-phenyl)ethyl]-α-phenyl-1H-1,2,4-triazole-1-propanenitrile(Proc. Br. Crop Prot. Conf. 1988—Pests Dis. Vol. 1, p. 33);fluquinconazole,3-(2,4-dichlorophenyl)-6-fluoro-2-[1,2,4]-triazol-1-yl-3H-quinazolin-4-one(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992)); flusilazole,1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1H-[1,2,4]triazole (Proc.Br. Crop Prot. Conf.-Pests Dis., 1, 413 (1984)); flutriafol,α-(2-fluorophenyl)-α-(4-fluorophenyl)-1H-1,2,4-triazole-1-ethanol (EP 15756); hexaconazole,2-(2,4-dichlorophenyl)-1-[1,2,4]triazol-1-ylhexan-2-ol (CAS RN79983-71-4); ipconazole,2-[(4-chlorophenyl)methyl]-5-(1-methylethyl)-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol(EP 267 778), metconazole,5-(4-chlorobenzyl)-2,2-dimethyl-1-[1,2,4]triazol-1-ylmethyl-cyclopentanol(GB 857 383); myclobutanil,2-(4-chlorophenyl)-2-[1,2,4]triazol-1-yl-methylpentanenitrile (CAS RN88671-89-0); penconazole,1-[2-(2,4-dichlorophenyl)-pentyl]-1H-[1,2,4]triazole (Pesticide Manual,12th Ed. (2000), S.712); propiconazole,1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole(BE 835 579); prochloraz,N-(propyl-[2-(2,4,6-trichlorophenoxy)ethyl])imidazole-1-carboxamide(U.S. Pat. No. 3,991,071); prothioconazole,2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]triazole-3-thione(WO 96/16048); simeconazole,α-(4-fluorophenyl)-α-[(trimethylsilyl)methyl]-1H-1,2,4-triazole-1-ethanol[CAS RN 149508-90-7]; tebuconazole,1-(4-chlorophenyl)-4,4-dimethyl-3-[1,2,4]triazol-1-ylmethylpentan-3-ol(EP-A 40 345); tetraconazole,1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-1,2,4-triazole(EP 234 242); triadimefon,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone(BE 793 867); triadimenol,β-(4-chlorophenoxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(DE 23 24 010); triflumizol,(4-chloro-2-trifluoromethylphenyl)-(2-propoxy-1-[1,2,4]triazol-1-ylethyliden)-amine(JP-A 79/119 462); triticonazole,(5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol(FR 26 41 277); iprodione,N-isopropyl-3-(3,5-dichlorophenyl)-2,4-dioxoimidazolidine-1-carboxamide(GB 13 12 536); myclozolin,(RS)-3-(3,5-dichlorophenyl)-5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione[CAS RN 54864-61-8]; procymidone,N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide (U.S.Pat. No. 3,903,090); vinclozolin,3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione (DE-A 22 07576); ferbam, iron(3+) dimethyldithiocarbamate (U.S. Pat. No.1,972,961); nabam, disodium ethylenebis-(dithiocarbamate) (U.S. Pat. No.2,317,765); maneb, manganese ethylenebis(dithiocarbamate) (U.S. Pat. No.2,504,404); mancozeb, manganese ethylenebis(dithiocarbamate) polymercomplex zinc salt (GB 996 264); metam, methyldithiocarbaminic acid (U.S.Pat. No. 2,791,605); metiram, zinc ammoniateethylenebis(dithiocarbamate) (U.S. Pat. No. 3,248,400); propineb, zincpropylenebis-(dithiocarbamate) polymer (BE 611 960); polycarbamate,bis(dimethylcarbamo-dithioato-S,S′)[μ-[[1,2-ethanediylbis[carbamodithioato-S,S′]](2−)]]di[zinc][CAS RN 64440-88-6]; thiram, bis(dimethylthiocarbamoyl) disulfide (DE642 532); ziram, dimethyldithiocarbamate [CAS RN 137-30-4]; zineb, zincethylenebis(dithiocarbamate) (U.S. Pat. No. 2,457,674); anilazine,4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazine-2-amine (U.S. Pat. No.2,720,480); benomyl, N-butyl-2-acetylaminobenzoimidazole-1-carboxamide(U.S. Pat. No. 3,631,176); boscalid,2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide (EP-A 545 099);carbendazim, methyl (1H-benzoimidazol-2-yl)carbamate (U.S. Pat. No.3,657,443); carboxin,5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (U.S. Pat. No.3,249,499); oxycarboxin,5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (U.S. Pat.No. 3,399,214); cyazofamid,4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide(CAS RN 120116-88-3]; dazomet, 3,5-dimethyl-1,3,5-thiadiazinane-2-thione(Bull. Soc. Chim. Fr. 15, p. 891 (1897)); dithianon,5,10-dioxo-5,10-dihydronaphtho[2,3-b][1,4]dithiin-2,3-dicarbonitrile (GB857 383); famoxadone,(RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione[CAS RN 131807-57-3]; fenamidone,(S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS RN161326-34-7]; fenarimol,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol (GB 12 18623); fuberidazole, 2-(2-furanyl)-1H-benzimidazole (DE 12 09 799);flutolanil, α,α,α-trifluoro-3′-isopropoxy-o-toluanilide (JP 1104514);furametpyr,5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1H-pyrazole-4-carboxamide[CAS RN 123572-88-3]; isoprothiolane, diisopropyl1,3-dithiolan-2-ylidenemalonate (Proc. Insectic. Fungic. Conf. 8. Vol.2, p. 715 (1975)); mepronil, 3′-isopropoxy-o-toluanilide (U.S. Pat. No.3,937,840); nuarimol,α-(2-chlorophenyl)-α-(4-fluorophenyl)-5-pyrimidinemethanol (GB 12 18623); fluopicolide (picobenzamid),2,6-dichloro-N-(3-chloro-5-trifluoromethylpyridin-2-ylmethyl)benzamide(WO 99/42447); probenazole, 3-allyloxy-1,2-benzothiazole 1,1-dioxide(Agric. Biol. Chem. 37, p. 737 (1973)); proquinazid,6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO 97/48684); pyrifenox,2′,4′-dichloro-2-(3-pyridyl)acetophenone (EZ)—O-methyloxime (EP 49 854);pyroquilon, 1,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-4-one (GB 139 43373) quinoxyfen, 5,7-dichloro-4-(4-fluorophenoxy)quinoline (U.S. Pat.No. 5,240,940); silthiofam,N-allyl-4,5-dimethyl-2-(trimethylsilyl)thiophene-3-carboxamide [CAS RN175217-20-6]; thiabendazole, 2-(1,3-thiazol-4-yl)benzimidazole (U.S.Pat. No. 3,017,415); thifluzamide,2′,6′-dibromo-2-methyl-4′-tri-fluormethoxy-4-trifluormethyl-1,3-thiazole-5-carboxanilide[CAS RN 130000-40-7]; thiophanate-methyl,1,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-A 19 30540); tiadinil,3′-chloro-4,4′-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN223580-51-6]; tricyclazole,5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole [CAS RN 41814-78-2];triforine,N,N′-{piperazine-1,4-diylbis[(trichlormethyl)methylene]}diformamide (DE19 01 421); Bordeaux mixture, mixture of CuSO₄×3Cu(OH)₂×3CaSO₄ [CAS RN8011-63-0]; copper acetate, Cu(OCOCH₃)₂ [CAS RN 8011-63-0]; copperoxychloride, Cu₂Cl(OH)₃ [CAS RN 1332-40-7]; basic copper sulfate, CuSO₄[CAS RN 1344-73-6]; binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl3-methylcrotonate [CAS RN 485-31-4]; dinocap, mixture of2,6-dinitro-4-octylphenylcrotonate and2,4-dinitro-6-octylphenylcrotonate, where “octyl” is a mixture of1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (U.S. Pat. No.2,526,660); dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate [CAS RN 973-21-7]; nitrothal-isopropyl, diisopropyl5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf. 7., Vol. 2, p.673 (1973)); fenpiclonil,4-(2,3-dichloro-phenyl)-1H-pyrrole-3-carbonitrile (Proc. 1988 Br. CropProt. Conf.—Pests Dis., Vol. 1, p. 65); fludioxonil,4-(2,2-difluorobenzo[1,3]dioxol-4-yl)-1H-pyrrole-3-carbonitrile (ThePesticide Manual, publ. The British Crop Protection Council, 10th ed.(1995), p. 482); acibenzolar-S-methyl, methyl1,2,3-benzothiadiazol-7-carbothioate [CAS RN 135158-54-2];flubenthiavalicarb (benthiavalicarb), isopropyl{(S)-1-[(1R)-1-(6-fluorobenzo-thiazol-2-yl)-ethylcarbamoyl]-2-methylpropyl}carbamate(JP-A 09/323 984); carpropamid,2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarboxamide[CAS RN 104030-54-8]; chlorothalonil,2,4,5,6-tetrachloroisophthalonitrile (U.S. Pat. No. 3,290,353);cyflufenamid,(Z)—N-[α-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoro-methyl)benzyl]-2-phenylacetamide(WO 96/19442); cymoxanil, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea(U.S. Pat. No. 3,957,847); diclomezine,6-(3,5-dichlorophenyl-p-tolyl)-pyridazin-3(2H)-one (U.S. Pat. No.4,052,395) diclocymet,(RS)-2-cyano-N—[(R)-1-(2,4-dichloro-phenyl)ethyl]-3,3-dimethylbutyramide[CAS RN 139920-32-4]; diethofencarb, isopropyl 3,4-diethoxycarbanilate(EP 78 663); edifenphos, O-ethyl S,S-diphenyl phosphoro-dithioate (DE 1493 736) ethaboxam,N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide(EP-A 639 574); fenhexamid,N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide (Proc.Br. Crop Prot. Conf.—Pests Dis., 1998, Vol. 2, p. 327); fentin acetate,triphenyltin (U.S. Pat. No. 3,499,086); fenoxanil,N-(1-cyano-1,2-di-methylpropyl)-2-(2,4-dichlorophenoxy)propanamide (EP262 393); ferimzone, mepanipyrim,(Z)-2′-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN89269-64-7]; fluazinam,3-chloro-N-[3-chloro-2,6-dinitro-4-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-2-pyridinamine(The Pesticide Manual, publ. The British Crop Protection Council, 10thed. (1995), p. 474); fosetyl, fosetyl-aluminum, ethylphosphonate (FR 2254 276); iprovalicarb, isopropyl[(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]-carbamate (EP-A 472996); hexachlorbenzene (C. R. Seances Acad. Agric. Fr. 31, p. 24, 1945);metrafenon, 3′-bromo-2,3,4,6′-tetramethoxy-2′,6-dimethylbenzophenone(U.S. Pat. No. 5,945,567); pencycuron,1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (DE 27 32 257);penthiopyrad,(RS)—N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide(JP 10130268); propamocarb, propyl 3-(dimethyl-amino)propylcarbamate (DE15 67 169); phthalide (DE 16 43 347); toloclofos-methyl,O-2,6-dichloro-p-tolyl O,O-dimethyl phosphorothioate (GB 14 67 561);quintozene, pentachlornitrobenzene (DE 682 048); zoxamide,(RS)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide[CAS RN 156052-68-5]; azoxystrobin, methyl2-{2-[6-(2-cyano-1-vinylpenta-1,3-dienyloxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate(EP 382 375), dimoxystrobin,(E)-2-(methoxyimino)-N-methyl-2-[α-(2,5-xylyl-oxy)-o-tolyl]acetamide (EP477 631); enestroburin, methyl2-{2-[3-(4-chlorophenyl)-1-methylallylideneaminooxymethyl]phenyl}-3-methoxyacrylate(EP 936 213); fluoxastrobin,(E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime (WO 97/27189); kresoxim-methyl, methyl(E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate (EP 253 213);metominostrobin,(E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP 398 692);orysastrobin,(2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8-dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide(WO 97/15552); picoxystrobin, methyl3-methoxy-2-[2-(6-trifluoromethylpyridin-2-yloxy-methyl)phenyl]acrylate(EP 278 595); pyraclostrobin, methylN-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carbamate(WO 96/01256); trifloxystrobin, methyl(E)-methoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylidene-aminooxy]o-tolyl}acetate(EP 460 575); captafol,N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide(Phytopathology, Vol. 52, p. 754 (1962)); captan,N-(tri-chloromethylthio)cyclohex-4-ene-1,2-dicarboximide (U.S. Pat. No.2,553,770); dichlofluanid,N-di-chlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide (DE 11 93498); folpet, N-(trichloromethylthio)phthalimide (U.S. Pat. No.2,553,770); tolylfluanid,N-dichlorofluoromethyl-thio-N′,N′-dimethyl-N-p-tolylsulfamide (DE 11 93498); dimethomorph,3-(4-chloro-phenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-yl-propenone(EP 120 321); flumetover,2-(3,4-dimethoxyphenyl)-N-ethyl-α,α,α-trifluoro-N-methyl-p-toluamide[AGROW no. 243, 22 (1995)]; flumorph,3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone (EP860 438);5-Amino-2-isopropyl-3-oxo-4-o-tolyl-2,3-dihydro-pyrazole-1-carbothioicacid S-allyl ester (CN1939128).

The compounds described by IUPAC nomenclature, their preparation andtheir fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6),587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970;EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S. Pat. No.3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO06/87343; WO 07/82098; WO 07/90624, WO 11/028657).N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamidehas been described in WO 2007/014290.

It is preferred that the compositions comprise as compounds V fungicidalcompounds that are independently of each other selected from the groupsof fungicides A), B), C), D), E), F), G), H), I), J), K) and L).

Preference is given to mixtures comprising as compound V at least oneactive substance selected from group A) and particularly selected fromazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin;famoxadone, fenamidone; bixafen, boscalid, fluopyram, fluxapyroxad,isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid,fluazinam, fentin salts, such as fentin acetate.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group B) and particularly selectedfrom cyproconazole, difenoconazole, epoxiconazole, fluquinconazole,flusilazole, flutriafol, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole,tetraconazole, triticonazole, prochloraz, fenarimol, triforine;dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;fenhexamid.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group C) and particularly selectedfrom metalaxyl, (metalaxyl-M) mefenoxam, ofurace.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group D) and particularly selectedfrom benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide,zoxamide, metrafenone, pyriofenone.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group E) and particularly selectedfrom cyprodinil, mepanipyrim, pyrimethanil.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group F) and particularly selectedfrom iprodione, fludioxonil, vinclozolin, quinoxyfen.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group G) and particularly selectedfrom dimethomorph, flumorph, iprovalicarb, benthiavalicarb,mandipropamid, propamocarb.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group H) and particularly selectedfrom copper acetate, copper hydroxide, copper oxychloride, coppersulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet,chlorothalonil, dichlofluanid, dithianon.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group I) and particularly selectedfrom carpropamid and fenoxanil.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group J) and particularly selectedfrom acibenzolar-S-methyl, probenazole, tiadinil, fosetyl,fosetyl-aluminium, H₃PO₃ and salts thereof.

Preference is also given to mixtures comprise as compound V at least oneactive substance selected from group K) and particularly selected fromcymoxanil, proquinazid andN-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.

Preference is also given to mixtures comprising as compound V at leastone active substance selected from group L) and particularly selectedfrom Bacillus subtilis strain NRRL No. B-21661, Bacillus pumilus strainNRRL No. B-30087 and Ulocladium oudemansii.

More preference is given to following compounds V: pyraclostrobin,epoxiconazole,2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl¬methyl]-2H[1,2,4]triazole-3-thiol and fluxapyroxade.

Specific compositions contain following fungicides:

An imidazolium compound F15 or F19 (formulae see in the examples) and acompound V selected from pyraclostrobin, epoxiconazole,2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl¬methyl]-2H[1,2,4]triazole-3-thiol and fluxapyroxade.

More specific compositions contain following fungicides:

An imidazolium compound F15 and a compound V selected frompyraclostrobin, epoxiconazole,2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl¬methyl]-2H[1,2,4]triazole-3-thiol and fluxapyroxade;

an imidazolium compound F19 and a compound V selected from epoxiconazoleand2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl¬methyl]-2H[1,2,4]triazole-3-thiol.

The polymeric, ionic compound comprising imidazolium groups and thefungicidal compositions according to the invention containing it aresuitable as fungicides. They are distinguished by an outstandingeffectiveness against a broad spectrum of phytopathogenic fungi,including soil-borne fungi, which derive especially from the classes ofthe Plasmodiophoromycetes, Peronosporomycetes (syn. Oomyce¬tes),Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes (syn. Fungi imperfecti). Some are systemically effectiveand they can be used in crop protection as foliar fungicides, fungicidesfor seed dressing and soil fungicides. Moreover, they are suitable forcontrolling harmful fungi, which inter alia occur in wood or roots ofplants.

The polymeric, ionic compound comprising imidazolium groups and thefungicidal compositions according to the invention containing it areparticularly important in the control of a multitude of phytopathogenicfungi on various cultivated plants, such as cereals, e.g. wheat, rye,barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet;fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries,blackberries or gooseberries; leguminous plants, such as lentils, peas,alfalfa or soy¬beans; oil plants, such as rape, mustard, olives,sunflowers, coconut, cocoa beans, castor oil plants, oil palms, groundnuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiberplants, such as cotton, flax, hemp or jute; citrus fruit, such asoranges, lemons, grapefruits or mandarins; vegetables, such as spinach,lettuce, aspa¬ragus, cabbages, carrots, onions, tomatoes, potatoes,cucurbits or paprika; laura¬ceous plants, such as avocados, cinnamon orcamphor; energy and raw material plants, such as corn, soybean, rape,sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bana¬nas;vines (table grapes and grape juice grape vines); hop; turf; naturalrubber plants or ornamental and forestry plants, such as flowers,shrubs, broad-leaved trees or ever¬greens, e.g. conifers; and on theplant propagation material, such as seeds, and the crop material ofthese plants.

Preferably the polymeric, ionic compound comprising imidazolium groupsand the fungicidal compositions according to the invention containing itare used for controlling a multitude of fungi on field crops, such aspotatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn,cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane;fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes,beans or squashes.

The term “plant propagation material” is to be understood to denote allthe genera¬give parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e.g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants,including seedlings and young plants, which are to be transplan¬tedafter germi¬nation or after emergence from soil. These young plants mayalso be protected before transplantation by a total or partial treatmentby immersion or pouring.

Preferably, treatment of plant propagation materials with the polymeric,ionic compound comprising imidazolium rings and compositions thereof,respectively, is used for controlling a multitude of fungi on cereals,such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or genetic engineeringincluding but not limiting to agricultural biotech products on themarket or in development (cf.http://www.bio.org/speeches/pubs/er/agri_products.asp). Geneticallymodified plants are plants, which genetic material has been so modifiedby the use of recombi¬nant DNA techniques that under naturalcircumstances cannot readily be obtained by cross breeding, mutations ornatural recombination. Typically, one or more genes have been integratedinto the genetic material of a genetically modified plant in order toimprove certain properties of the plant. Such genetic modifications alsoinclude but are not limited to targeted post-transtional modification ofprotein(s), oligo- or polypeptides e.g. by glycosylation or polymeradditions such as prenylated, acetylated or farnesylated moieties or PEGmoieties.

Plants that have been modified by breeding, mutagenesis or geneticengineering, e.g. have been rendered tolerant to applications ofspecific classes of herbicides, such as hydroxyphenylpyruvatedioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors,such as sulfonyl ureas (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685,WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) orimidazolinones (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073);enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such asglyphosate (see e.g. WO 92/00377); glutamine synthetase (GS) inhibitors,such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynilherbicides (see e.g. U.S. Pat. No. 5,559,024) as a result ofconventional methods of breeding or genetic engineering. Severalcultivated plants have been rendered tolerant to herbicides byconventional methods of breeding (mutagenesis), e.g. Clearfield® summerrape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e.g.imazamox. Genetic engineering methods have been used to rendercultivated plants such as soybean, cotton, corn, beets and rape,tolerant to herbicides such as glypho¬sate and glufosinate, some ofwhich are commercially available under the trade names RoundupReady®(glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink®(glufosinate-tolerant, Bayer CropScience, Germany).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more insecticidal proteins,especially those known from the bacterial genus Bacillus, particularlyfrom Bacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b),CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c;vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;insecticidal proteins of bacteria colonizing nematodes, e.g.Photo¬irhab¬idus spp. or Xenorhabdus spp.; toxins produced by animals,such as scorpion toxins, arachnid toxins, wasp toxins, or otherinsect-specific neurotoxins; toxins produced by fungi, suchStreptomycetes toxins, plant lectins, such as pea or barley lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be under¬stood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, e.g. WO 02/015701). Further examples of such toxins or geneticallymodified plants capable of synthesizing such toxins are disclosed, e.g.,in EP A 374 753, WO 93/007278, WO 95/34656, EP A 427 529, EP A 451 878,WO 03/18810 and WO 03/52073. The methods for producing such geneticallymodified plants are generally known to the person skilled in the art andare described, e.g. in the publications mentioned above. Theseinsecticidal proteins contained in the genetically modified plantsimpart to the plants producing these proteins tolerance to harmful pestsfrom all taxonomic groups of athropods, especially to beetles(Coelop¬tera), two-winged insects (Diptera), and moths (Lepidoptera) andto nematodes (Nema¬toda). Genetically modified plants capable tosynthesize one or more insecticidal pro¬teins are, e.g., described inthe publications mentioned above, and some of which are commerciallyavailable such as YieldGard® (corn cultivars producing the Cry1Abtoxin), YieldGard® Plus (corn cultivars producing Cry1Ab and Cry3Bb1toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex®RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzymePhosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cottoncultivars producing the Cry1Ac toxin), Bollgard® I (cotton culti¬varsproducing the Cry1Ac toxin), Bollgard® II (cotton cultivars producingCry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing aVIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin);Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g.Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivarsproducing the Cry1Ab toxin and PAT enyzme), MIR604 from Syngenta SeedsSAS, France (corn cultivars producing a modified version of the Cry3Atoxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium(corn cultivars prod¬ucing the Cry3Bb1 toxin), IPC 531 from MonsantoEurope S.A., Belgium (cotton cultivars producing a modified version ofthe Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium(corn cultivars producing the Cry1F toxin and PAT enzyme).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to in¬creasethe resistance or tolerance of those plants to bacterial, viral orfungal pathogens. Examples of such proteins are the so-called“pathogenesis-related proteins” (PR proteins, see, e.g. EP A 392 225),plant disease resistance genes (e.g. potato culti¬vars, which expressresistance genes acting against Phytophthora infestans derived from themexican wild potato Solanum bulbocastanum) or T4-lyso¬zym (e.g. potatocultivars capable of synthesizing these proteins with increasedresistance against bacteria such as Erwinia amylvora). The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e.g. in the publicationsmentioned above.

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe productivity (e.g. bio mass production, grain yield, starch content,oil content or protein content), tolerance to drought, salinity or othergrowth-limiting environ¬mental factors or tolerance to pests and fungal,bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve human or animalnutrition, e.g. oil crops that produce health-promoting long-chainomega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera®rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve raw materialproduction, e.g. potatoes that produce increased amounts of amylopectin(e.g. Amflora® potato, BASF SE, Germany).

The polymeric, ionic compound comprising imidazolium groups and thefungicidal compositions according to the invention containing it areparticularly suitable for controlling the following plant diseases:Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. candida)and sun¬glowers (e.g. A. tragopogonis); Alternaria spp. (Alternaria leafspot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A.tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or A.alternata), tomatoes (e.g. A. solani or A. alternata) and wheat;Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. oncereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A.hordei on barley; Bipolaris and Drechslera spp. (teleomorph:Cochliobolus spp.) on corn (e.g. D. maydis), cereals (e.g. B.sorokiniana: spot blotch), rice (e.g. B. oryzae) and turfs; Blumeria(formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheator barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: greymold) on fruits and berries (e.g. strawberries), vegetables (e.g.lettuce, carrots, celery and cabbages), rape, flowers, vines, forestryplants and wheat; Bremia lactucae (downy mildew) on lettuce;Cerato¬cystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved treesand evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercosporaspp. (Cercospora leaf spots) on corn, rice, sugar beets (e.g. C.beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina orC. kikuchii) and rice; Cladosporium spp. on tomatoes (e.g. C. fulvum:leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Clavicepspurpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium ofBipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C.sativus, anamorph: B. sorokiniana) and rice (e.g. C. miyabeanus,anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp.(anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C. graminicola),soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C.lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides);Corticium spp., e.g. C. sasakii (sheath blight) on rice; Coryne¬sporacassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp.,e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit treecanker or young vine decline, teleomorph: Nectria or Neonectria spp.) onfruit trees, vines (e.g. C. lirio¬dendri, teleomorph: Neonectrialiriodendri: Black Foot Disease) and ornamentals; Dematophora(teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans;Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans;Drechs¬lera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. oncorn, cereals, such as barley (e.g. D. teres, net blotch) and wheat(e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback,apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F.mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremoniumchlamydo¬sporum), Phaeoacremonium aleophilum and/or Botryosphaeriaobtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta:anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leafsmut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp.(powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi),such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E.crucife¬rarum); Eutypa lata (Eutypa canker or dieback, anamorph:Cytosporina lata, syn. Liber¬tella blepharis) on fruit trees, vines andornamental woods; Exserohilum (syn. Helmin¬thosporium) spp. on corn(e.g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, rootor stem rot) on various plants, such as F. graminearum or F. culmorum(root rot, scab or head blight) on cereals (e.g. wheat or barley), F.oxysporum on tomatoes, F. solani on soybeans and F. verticillioides oncorn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat orbarley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice(e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines,pome fruits and other plants and G. gossypii on cotton; Grain¬stainingcomplex on rice; Guignardia bidwellii (black rot) on vines;Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae(rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph:Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H.vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn.Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli)(root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium)nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaeradiffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, M.fructicola and M. fructigena (bloom and twig blight, brown rot) on stonefruits and other rosaceous plants; Mycosphaerella spp. on cereals,bananas, soft fruits and ground nuts, such as e.g. M. graminicola(anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis(black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) oncabbage (e.g. P. brassicae), rape (e.g. P. parasitica), onions (e.g. P.destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica);Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans;Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora)and soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stemrot) on rape and cabbage and P. betae (root rot, leaf spot anddamping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e.g.P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P.phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brownspots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stemroot) on various plants, such as paprika and cucurbits (e.g. P.capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes andtomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g.P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) oncabbage, rape, radish and other plants; Plasmopara spp., e.g. P.viticola (grapevine downy mildew) on vines and P. halstedii onsunflowers; Podosphaera spp. (powdery mildew) on rosa¬ceous plants, hop,pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., e.g.on cereals, such as barley and wheat (P. graminis) and sugar beets (P.betae) and there¬by transmitted viral diseases; Pseudocercosporellaherpotrichoides (eyespot, teleo¬morph: Tapesia yallundae) on cereals,e.g. wheat or barley; Pseudoperonospora (downy mildew) on variousplants, e.g. P. cubensis on cucurbits or P. humili on hop;Pseudopezicula tracheiphila (red fire disease or ‘rotbrenner’, anamorph:Phialophora) on vines; Puccinia spp. (rusts) on various plants, e.g. P.triticina (brown or leaf rust), P. strihformis (stripe or yellow rust),P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita(brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, andasparagus (e.g. P. asparagi); Pyrenophora (anamorph: Drechslera)tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley;Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, riceblast) on rice and P. grisea on turf and cereals; Pythium spp.(damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers,soy¬beans, sugar beets, vegetables and various other plants (e.g. P.ultimum or P. aphani¬dermatum); Ramularia spp., e.g. R. collo-cygni(Ramularia leaf spots, Physiological leaf spots) on barley and R.beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes,turf, corn, rape, potatoes, sugar beets, vegetables and various otherplants, e.g. R. solani (root and stem rot) on soybeans, R. solani(sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) onwheat or barley; Rhizopus stolonifer (black mold, soft rot) onstrawberries, carrots, cabbage, vines and tomatoes; Rhynchosporiumsecalis (scald) on barley, rye and triticale; Sarocladium oryzae and S.attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or whitemold) on vegetables and field crops, such as rape, sunflowers (e.g. S.sclerotiorum) and soybeans (e.g. S. rolfsii or S. sclerotiorum);Septoria spp. on various plants, e.g. S. glycines (brown spot) onsoybeans, S. tritici (Septoria blotch) on wheat and S. (syn.Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines;Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn.Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn,(e.g. S. reiliana: head smut), sorghum and sugar cane; Sphaerothecafuliginea (powdery mildew) on cucurbits; Spongospora subterranea(powdery scab) on potatoes and thereby transmitted viral diseases;Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch,teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat;Synchytrium endobioticum on potatoes (potato wart disease); Taphrinaspp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni(plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco,pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn.Chalara elegans); Tilletia spp. (common bunt or stinking smut) oncereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T.controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) onbarley or wheat; Uro¬cystis spp., e.g. U. occulta (stem smut) on rye;Uromyces spp. (rust) on vege¬tables, such as beans (e.g. U.appendiculatus, syn. U. phaseoli) and sugar beets (e.g. U. betae);Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae),corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) onapples (e.g. V. inaequalis) and pears; and Verticillium spp. (wilt) onvarious plants, such as fruits and ornamentals, vines, soft fruits,vegetables and field crops, e.g. V. dahliae on straw¬berries, rape,potatoes and tomatoes.

The inventive mixtures and compositions are also suitable forcontrolling harmful fungi in the protection of stored products orharvest and in the protection of materials. The term “protection ofmaterials” is to be understood to denote the protection of technical andnon-living materials, such as adhesives, glues, wood, paper andpaperboard, textiles, leather, paint dispersions, plastics, coilinglubricants, fiber or fabrics, against the infestation and destruction byharmful microorganisms, such as fungi and bacteria. As to the protectionof wood and other materials, the particular attention is paid to thefollowing harmful fungi: Ascomycetes such as Ophiostoma spp.,Ceratocystis spp., Aureobasidium pullu¬lans, Sclerophoma spp.,Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.;Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllumspp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. andTyromyces spp., Deutero¬mycetes such as Aspergillus spp., Cladosporiumspp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomycesspp. and Zygomycetes such as Mucor spp., and in addition in theprotection of stored products and harvest the following yeast fungi areworthy of note: Candida spp. and Saccharomyces cerevisae. In particular,the mixtures and compositions of the present invention are effectiveagainst plant pathogens in speciality crops such as vine, fruits, hop,vegetables and tabacco—see the above list.

Plant propagation materials may be treated with the polymeric, ioniccompound comprising imidazolium groups and the fungicidal compositionsaccording to the invention containing it prophylactically either at orbefore planting or transplanting. The invention also relates toagrochemical compositions comprising an auxiliary and at least onepolymeric, ionic compound comprising imidazolium groups and at leastcompound V.

An agrochemical composition comprises a fungicidally effective amount ofthe at least one polymeric, ionic compound comprising imidazolium groupsand the at least compound V. The term “effective amount” denotes anamount of the composition or of the compounds, which is sufficient forcontrolling harmful fungi on cultivated plants or in the protection ofmaterials and which does not result in a substantial damage to thetreated plants. Such an amount can vary in a broad range and isdependent on various factors, such as the fungal species to becontrolled, the treated cultivated plant or material, the climaticconditions and the specific compounds used.

The polymeric, ionic compound comprising imidazolium groups can beconverted into customary types of agrochemical compositions, e.g.solutions, emulsions, suspensions, dusts, powders, pastes, granules,pressings, capsules, and mixtures thereof. Examples for compositiontypes are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g.EC), emul¬sions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes,pastilles, wettable pow¬ders or dusts (e.g. WP, SP, WS, DP, DS),pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG),insecticidal articles (e.g. LN), as well as gel formulations for thetreatment of plant propagation materials such as seeds (e.g. GF). Theseand further compositions types are defined in the “Catalogue ofpesticide formulation types and international coding system”, TechnicalMonograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described byMollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001;or Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers orfillers, surfactants, dispersants, emulsifiers, wetters, adjuvants,solubilizers, penetration enhancers, protective colloids, adhesionagents, thickeners, humectants, repellents, attractants, feedingstimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e.g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclo¬hexanol; glycols; DMSO; ketones,e.g. cyclo¬hexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid di¬methylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers,e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas;products of vegetable origin, e.g. cereal meal, tree bark meal, woodmeal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures there¬of. Such surfactants can be used asemusifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulf¬onates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulf¬onates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulf¬onates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkyl¬naphtha¬lenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxy¬lates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates. Suitable nonionic surfactants arealkoxylates, N-substituted fatty acid amides, amine oxides, esters,sugar-based surfactants, polymeric surfactants, and mixtures thereof.Examples of alkoxylates are compounds such as alcohols, alkylphenols,amines, amides, arylphenols, fatty acids or fatty acid esters which havebeen alkoxylated with 1 to 50 equivalents. Ethylene oxide and/orpropylene oxide may be employed for the alkoxylation, preferablyethylene oxide. Examples of N-substituted fatty acid amides are fattyacid glucamides or fatty acid alkanolamides. Examples of esters arefatty acid esters, glycerol esters or monoglycerides. Examples ofsugar-based surfactants are sorbitans, ethoxylated sorbitans, sucroseand glucose esters or alkylpolyglucosides. Examples of polymericsurfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols,or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary am¬monium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of poly¬ethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,poly¬ethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the polymeric, ionic compound comprising imidazoliumgroups on the target. Examples are surfactants, mineral or vegetableoils, and other auxilaries. Further examples are listed by Knowles,Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006,chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellu¬lose), anorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkyliso¬thiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are (wherein activesubstances denote at least one polymeric, ionic compound comprisingimidazolium groups and optionally compound V):

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % active substances and 5-15 wt % wetting agent (e.g. alcoholalkoxylates) are dissolved in water and/or in a water-soluble solvent(e.g. alcohols) ad 100 wt %. The active substance dissolves upondilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % active substances and 1-10 wt % dispersant (e.g.polyvinylpyrrolidone) are dissolved in organic solvent (e.g.cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.

iii) Emulsifiable Concentrates (EC)

15-70 wt % active substances and 5-10 wt % emulsifiers (e.g. calciumdodecylben¬zenesulfonate and castor oil ethoxylate) are dissolved inwater-insoluble organic sol¬vent (e.g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.

iv) Emulsions (EW, EO, ES)

5-40 wt % active substances and 1-10 wt % emulsifiers (e.g. calciumdodecylben¬zenesulfonate and castor oil ethoxylate) are dissolved in20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon).This mixture is introduced into water ad 100 wt % by means of anemulsifying machine and made into a homogeneous emul¬sion. Dilution withwater gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % active substances are comminutedwith addition of 2-10 wt % dispersants and wetting agents (e.g. sodiumlignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g.xanthan gum) and ad water ad 100 wt % to give a fine active substancesuspension. Dilution with water gives a stable suspension of the activesubstance. For FS type composition up to 40 wt % binder (e.g.polyvinylalcohol) is added.

vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50-80 wt % active substances are ground finely with addition ofdispersants and wetting agents (e.g. sodium lignosulfonate and alcoholethoxylate) ad 100 wt % and prepared as water-dispersible orwater-soluble granules by means of technical appliances (e.g. extrusion,spray tower, fluidized bed). Dilution with water gives a stabledispersion or solution of the active substance.

vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

50-80 wt % active substances are ground in a rotor-stator mill withaddition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt %wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silicagel) ad 100 wt %. Dilution with water gives a stable dispersion orsolution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % active substances are comminutedwith addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5wt % thickener (e.g. carboxy¬methylcellulose) and water ad 100 wt % togive a fine suspension of the active substance. Dilution with watergives a stable suspension of the active substance.

iv) Microemulsion (ME)

5-20 wt % active substances are added to 5-30 wt % organic solvent blend(e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactantblend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water ad100 wt %. This mixture is stirred for 1 h to produce spontaneously athermodynamically stable microemulsion.

iv) Microcapsules (CS)

An oil phase comprising 5-50 wt % active substances, 0-40 wt % waterinsoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylicmonomers (e.g. methylmethac¬rylate, methacrylic acid and a di- ortriacrylate) are dispersed into an aqueous solu¬tion of a protectivecolloid (e.g. polyvinyl alcohol). Radical polymerization initiated by aradi¬cal initiator results in the formation of poly(meth)acrylatemicrocapsules. Alternatively, an oil phase comprising 5-50 wt % of anactive compound, 0-40 wt % water insoluble organic solvent (e.g.aromatic hydrocarbon), and an isocyanate monomer (e.g.diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueoussolution of a protective colloid (e.g. polyvinyl alcohol). The additionof a polyamine (e.g. hexamethylenediamine) results in the formation ofpolyurea microcapsules. The mono¬mers amount to 1-10 wt %. The wt %relate to the total CS composition.

ix) Dustable Powders (DP, DS)

1-10 wt % active substances are ground finely and mixed intimately withsolid carrier (e.g. finely divided kaolin) ad 100 wt %.

x) Granules (GR, FG)

0.5-30 wt % active substances are ground finely and associated withsolid carrier (e.g. silicate) ad 100 wt %. Granulation is achieved byextrusion, spray-drying or fluidized bed.

xi) Ultra-Low Volume Liquids (UL)

1-50 wt % active substances are dissolved in organic solvent (e.g.aromatic hydro¬carbon) ad 100 wt %.

The compositions types i) to xi) may optionally comprise furtherauxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezingagents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.

The agrochemical compositions generally comprise between 0.01 and 95%,preferably between 0.1 and 90%, and in particular between 0.5 and 75%,by weight of active substance(s). The active substances are employed ina purity of from 90% to 100%, preferably from 95% to 100% (according toNMR spectrum).

Solutions for seed treatment (LS), suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40%, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying or treating the polymeric, ionic compoundcomprising imidazolium groups and the optional compound V andcompositions thereof, respectively, on to plant propagation material,especially seeds include dressing, coating, pelleting, dusting, soakingand in-furrow application methods of the propagation material.Preferably, the active compound(s) or the compositions thereof,respectively, are applied on to the plant propagation material by amethod such that germination is not induced, e.g. by seed dressing,pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e.g. bydusting, coating or drenching seed, amounts of active substance of from0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to100 g and most preferably from 5 to 100 g, per 100 kilogram of plantpropagation material (preferably seed) are generally required. When usedin the protection of materials or stored products, the amount of activesubstance applied depends on the kind of application area and on thedesired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material. Various types of oils,wetters, adjuvants, fertilizer, or micronutrients, and furtherpesticides (e.g. herbicides, insecticides, fungicides, growthregulators, safeners) may be added to the active substances or thecompositions comprising them as premix or, if appropriate not untilimmediately prior to use (tank mix). These agents can be admixed withthe compositions according to the invention in a weight ratio of 1:100to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank andfurther auxiliaries may be added, if appropriate.

In the compositions according to the invention containing at least onecompound V, the total weight ratio of polymeric, ionic compound(s)comprising imidazolium groups and compound(s) V generally depends fromthe properties of the active substances used, usually it is in the rangeof from 1:100 to 100:1, regularly in the range of from 1:80 to 80:1,preferably in the range of from 1:50 to 50:1, more preferably in therange of from 1:20 to 20:1, even more preferably in the range of from1:10 to 10:1 and in particular in the range of from 1:4 to 4:1.

According to further embodiments of the compositions according to theinvention containing at least one compound V, the total weight ratio ofpolymeric, ionic compound(s) comprising imidazolium groups andcompound(s) V usually is in the range of from 100:1 to 1:1, regularly inthe range of from 80:1 to 1:1, preferably in the range of from 50:1 to1:1, more preferably in the range of from 20:1 to 1:1, even morepreferably in the range of from 10:1 to 1:1 and in particular in therange of from 4:1 to 1:1.

According to further embodiments of the compositions according to theinvention containing at least one compound V, the total weight ratio ofpolymeric, ionic compound(s) comprising imidazolium groups andcompound(s) V usually is in the range of from 1:1 to 1:100, regularly inthe range of from 1:1 to 1:80, preferably in the range of from 1:1 to1:50, more preferably in the range of from 1:1 to 1:20, even morepreferably in the range of from 1:1 to 1:10 and in particular in therange of from 1:1 to 1:4.

Any further active components are, if desired, added in a ratio of from20:1 to 1:20 to the polymeric, ionic compound(s) comprising imidazoliumgroups.

In the mixtures and compositions, the compound ratios (e.g. polymeric,ionic compound(s) comprising imidazolium groups/compound V ratio) areadvantageously chosen so as to produce a synergistic effect, i.e. in thefungicidal composition, the fungicidal use and method of the presentinvention the composition preferably contains the at least oneimidazolium compound and the at least one compound V in synergisticallyeffective amounts. This means that the relative amount, i.e. the weightratio of the at least one imidazolium compound A and the at least onecompound V in the composition, provides for an increased fungicidalefficacy on at least one harmful fungus which exceeds the additivefungicidal efficacy of the compounds of the composition as calculatedfrom the fungicidal efficacy of the individual compounds at a givenapplication rate. The calculation of the additive efficacies can beperformed e.g. by Colby's formula (Colby, S. R. “Calculating synergisticand antagonistic responses of herbicide Combinations”, Weeds, 15, 20-22,1967). Synergism is present if the observed efficacy is greater than thecalculated efficacy.

The term “synergistic effect” is also understood to refer to thatdefined by application of the Tammes method, (Tammes, P. M. L.,“Isoboles, a graphic representation of synergism in pesticides”,Netherl. J. Plant Pathol. 70, 1964).

To ensure synergism, the at least one imidazolium compound and the atleast one compound V are preferably present in the compositions of thepresent invention in a total weight ratio as already indicated above,i.e. of from 100:1 to 1:100, more preferably from 80:1 to 1:80, evenmore preferably from 50:1 to 1:50, and in particular from 20:1 to 1:20.

The components can be used individually or already partially orcompletely mixed with one another to prepare the composition accordingto the invention. It is also possible for them to be packaged and usedas combination such as a kit of parts.

The fungicidal action of the compositions according to the invention canbe shown by the tests described below.

The active compounds, separately or jointly, are prepared as a stocksolution comprising 25 mg of active compound which is made up to 10 mlusing a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL(wetting agent having an emulsifying and dispersing action based onethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of99:1. The mixture is then made up to 100 ml with water. This stocksolution is diluted with the solvent/emulsifier/water mixture describedto give the concentration of active compound stated below.

The visually determined percentages of infected leaf areas are convertedinto efficacies in % of the untreated control.

The efficacy (E) is calculated as follows using Abbot's formula:

E=(1−α/β)·100

α corresponds to the fungicidal infection of the treated plants in % andβ corresponds to the fungicidal infection of the untreated (control)plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of active compound combinations were determinedusing Colby's formula (Colby, S. R. “Calculating synergistic andantagonistic responses of herbicide combinations”, Weeds, 15, pp. 20-22,1967) and compared with the observed efficacies.

E=x+y−x·y/100  Colby's formula:

-   E expected efficacy, expressed in % of the untreated control, when    using the mixture of the active compounds A and B at the    concentrations a and b-   x efficacy, expressed in % of the untreated control, when using the    active compound A at the concentration a-   y efficacy, expressed in % of the untreated control, when using the    active compound B at the concentration b.

In another aspect, the invention relates to a method for combatingharmful fungi, which method comprises treating the fungi or materials,plants, parts thereof, the locus where the plants grow or are to grow orplants' propagation material to be protected from fungal attack with aneffective amount of at least one polymeric, ionic compound comprisingimidazolium groups (imidazolium compound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal.

In another aspect, the invention relates to the use of at least onepolymeric, ionic compound comprising imidazolium groups (imidazoliumcompound), obtainable by reacting

a) at least one α-dicarbonyl compound,b) at least one aldehyde,c) at least one amino compound having at least two primary amino groups,d) optionally an amino compound having only one primary amino group ande) at least one protic acid,and optionally subjecting the reaction product to an anion exchange,where in the components a) and b) the aldehyde carbonyl groups may alsobe present as hemiacetal or acetal and the ketone carbonyl groups mayalso be present as hemiketal or ketal;for combating harmful fungi.

Preferably, the main chain of the at least one compound comprisingimidazolium groups does not contain 1,4-bound phenylene rings; and/orthe main chain of the at least one imidazolium compound apart from thenitrogen atoms of the imidazolium groups does not contain any quaternarynitrogen atoms that bear 4 residues that are different from hydrogen;and/or the amino compound having at least two primary amino groups isnot 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane; and/or the polymer comprises atleast 8 imidazolium rings.

In one preferred embodiment, the amino compound having at least twoprimary amino groups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane.

In another embodiment, the polymer comprises at least 8, preferably atleast 10 imidazolium rings.

In another embodiment, the main chain of the at least one compoundcomprising imidazolium groups does not contain 1,4-bound phenylene rings

In another embodiment, the main chain of the at least one imidazoliumcompound apart from the nitrogen atoms of the imidazolium groups doesnot contain any quaternary nitrogen atoms that bear 4 residues that aredifferent from hydrogen.

In one preferred embodiment, the amino compound having at least twoprimary amino groups is not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane and the polymer comprises atleast 8, preferably at least 10 imidazolium rings.

In particular, the polymer has one of the general or preferred meaningsgiven above in context with the biocidal composition, and the fungicidalcomposition has one of the general or preferred meanings given above forthe biocidal composition; i.e. the above-described biocidal compositionis preferably a fungicidal composition.

In a specific embodiment, the composition contains at least one furtheragrochemically active compound V.

As regards suitable and preferred polymers, compositions, compounds V,fungi, plants and ways of using the polymers and compositions, referenceis made to what has been said above.

Personal Care Composition

A further aspect of the invention is a personal care composition,comprising

-   A) at least one polymeric, ionic compound comprising imidazolium    groups (imidazolium compound), obtainable by reacting    -   a) at least one α-dicarbonyl compound,    -   b) at least one aldehyde,    -   c) at least one amino compound having at least two primary amino        groups,    -   d) optionally an amino compound having only one primary amino        group and    -   e) at least one protic acid,    -   and optionally subjecting the reaction product to an anion        exchange,    -   where the main chain of the at least one compound comprising        imidazolium groups does not contain 1,4-bound benzene rings,        specifically does not contain benzene rings, and    -   where in the components a) and b) the aldehyde carbonyl groups        may also be present as hemiacetal or acetal and the ketone        carbonyl groups may also be present as hemiketal or ketal,-   C) optionally at least one cosmetically acceptable active    ingredient, and-   D) optionally at least one cosmetically acceptable auxiliary.

Preferably, the main chain of the at least one imidazolium compoundapart from the nitrogen atoms of the imidazolium groups does not containany quaternary nitrogen atoms that bear 4 residues that are differentfrom hydrogen, either.

Suitable personal care compositions are cosmetic compositions andhygiene compositions. With regard to suitable and preferred embodimentsof the imidazolium compound A), reference is made to the generaldefinition of the imidazolium compound as defined above. Suitable andpreferred embodiments of the compounds B) and C) are mentioned in thefollowing.

—Personal Care Composition Containing Imidazolium Compounds asMicrobiocide

The personal care composition according to the invention can be acomposition that is effective against various microorganisms. Thus, in afirst variant, the personal care composition comprises at least oneimidazolium compound as microbiocide. The personal care compositionsaccording this variant contains at least one imidazolium compound A),alone or in combination with at least one further microbicidal compoundB), present at a concentration effective to confer an antimicrobialeffect on a person to whom it is applied. According to this variant, theimidazolium compound itself (=component A) may also act as cosmeticallyactive ingredient. Accordingly, in such a composition the use of afurther cosmetically acceptable active ingredient C) is only optional.

In a special embodiment, the invention relates to a personal carecomposition comprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one cosmetically acceptable active    ingredient, and-   D) optionally at least one cosmetically acceptable auxiliary,    wherein the composition contains components A) and optionally B) in    an antimicrobicidal effective amount.

An antimicrobicidal effective amount denotes an amount that issufficient to reduce the cell population of an unwanted microorganism orseveral unwanted microorganisms under a predetermined threshold value.

The personal care composition may comprise at least one imidazoliumcompound A) as the sole antimicrobicidal effective component. Then, thepersonal care composition preferably comprises the at least oneimidazolium compound A) in an amount of from 0.01 to 10 wt %, morepreferably 0.05 to 5 wt %, in particular 0.1 to 1 wt %, based on thetotal weight of the composition. The personal care composition may alsocomprise at least one imidazolium compound A) and at least one furthermicrobicidal compound B) different from the compounds A) as theantimicrobicidal effective components. Then, the personal carecomposition preferably comprises the sum of components A) and B) in anamount of from 0.01 to 10 wt %, more especially 0.05 to 5 wt %, inparticular 0.1 to 1 wt %, based on the total weight of the composition.

—Personal Care Composition Containing Imidazolium Compounds asPreservative

In a second variant, the personal care composition comprises at leastone imidazolium compound as preservative. The personal care compositionaccording to this variant contains at least one imidazolium compound A),alone or in combination with at least one further microbicidal compoundB), present at a concentration effective to preserve the compositionagainst microbes. Such compositions are usually non-toxic,cost-effective and shelf-stable over prolonged periods. In such acomposition the imidazolium compound itself (=component A) usually doesnot act as cosmetically active ingredient. Thus, in the personal carecomposition according to this second variant the use of a furthercosmetically acceptable active ingredient C) is usually mandatory.

A further aspect of the invention is a personal care compositioncomprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one cosmetically acceptable active    ingredient, and-   D) optionally at least one cosmetically acceptable auxiliary,    wherein the composition contains components A) and optionally B) in    a preservative effective amount.

A preservative effective amount denotes an amount that is sufficient toreduce the cell population of an unwanted microorganism under apredetermined threshold value to obtain shelf-stability over a certainperiod of time. Thus, a “preservative-effective amount” can be e.g.defined as an amount sufficient to reduce the cell population by threelog orders of the five following microorganisms: Staphylococcus aureus,Pseudomonas aeruginosa, Eschrechia coli, Candida albicans andAspergillus niger.

The personal care composition may comprise at least one imidazoliumcompound A) as the sole preservative effective component. Then, thepersonal care composition preferably comprises the at least oneimidazolium compound A) in an amount of from 0.00001 to 10 wt %, morepreferably 0.0001 to 5 wt %, in particular 0.001 to 1 wt %, based on thetotal weight of the composition. The personal care composition may alsocomprise at least one imidazolium compound A) and at least one furthermicrobicidal compound B) different from the compounds A) as thepreservative effective components. Then, the personal care compositionpreferably comprises the sum of components A) and B) in an amount offrom 0.01 to 10 wt %, more especially 0.05 to 5 wt %, in particular 0.1to 1 wt %, based on the total weight of the composition.

—Personal Care Composition Containing Imidazolium Compounds to Perform aFunction in the Final Product Different from the Function asMicrobiocide or Preservative

The imidazolium compounds according to the invention can also beadvantageously employed to perform a function in the final productdifferent from the function as microbiocide or preservative. Theimidazolium compounds may perform this function as an alternative to orin addition to the function as microbiocide or preservative.

Suitable personal care compositions are:

-   -   skin-care preparations, e.g. skin-washing and cleansing        preparations in the form of tablets, liquid soaps, bar soaps,        syndets, washing gels, soapless detergents or washing pastes,    -   bath preparations, e.g. liquid (foam baths, milks, oils, shower        preparations) or solid bath preparations, e.g. bath cubes and        bath salts;    -   skin-care preparations, e.g. skin emulsions, multi-emulsions,        powders, sprays or skin oils;    -   cosmetic personal care preparations, e.g. facial make-up in the        form of day creams or powder creams, face powder (loose or        pressed), rouge or cream make-up, eye-care preparations, e.g.        eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix        creams; lip-care preparations, e.g. lipsticks, lip gloss, lip        contour pencils, nail-care preparations, such as nail varnish,        nail varnish removers, nail hardeners or cuticle removers;    -   foot-care preparations, e.g. foot baths, foot powders, foot        creams or foot balsams, special deodorants and antiperspirants        or callus-removing preparations;    -   light-protective preparations, such as sun milks, lotions,        creams or oils, sunblocks or tropicals, pre-tanning preparations        or after-sun preparations;    -   skin-tanning preparations, e.g. self-tanning creams;    -   depigmenting preparations, e.g. preparations for bleaching the        skin or skin-lightening preparations;    -   insect-repellents, e.g. insect-repellent oils, lotions, sprays        or sticks;    -   deodorants, such as deodorant sprays, deodorant aerosols,        pump-action sprays, deodorant gels, sticks or roll-ons, also        water-free deodorant aerosols or sticks;    -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons,        also water-free antiperspirant aerosols and water-free        antiperspirant sticks;    -   preparations for cleansing and caring for blemished skin, e.g.        synthetic detergents (solid or liquid), peeling or scrub        preparations or peeling masks;    -   hair-removal preparations in chemical form (depilation), e.g.        hair-removing powders, liquid hair-removing preparations, cream-        or paste-form hair-removing preparations, hair-removing        preparations in gel form or aerosol foams;    -   shaving preparations, e.g. shaving soap, foaming shaving creams,        non-foaming shaving creams, foams and gels, pre-shave        preparations for dry shaving, aftershaves or aftershave lotions;    -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de        toilette, eau de parfum, parfum de toilette, perfume), perfume        oils or perfume creams;    -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pretreatment preparations, hair tonics,        styling creams, styling gels, pomades, hair rinses, treatment        packs, intensive hair treatments, hair-structuring preparations,        e.g. hair-waving preparations for permanent waves (hot wave,        mild wave, cold wave), hair-straightening preparations, liquid        hairsetting preparations, hair foams, hairsprays, bleaching        preparations, e.g. hydrogen peroxide solutions, lightening        shampoos, bleaching creams, bleaching powders, bleaching pastes        or oils, temporary, semi-permanent or permanent hair colorants,        preparations containing self-oxidising dyes, or natural hair        colorants, such as henna or camomile.    -   antidandruff preparations in the form of shampoos, conditioners,        hair tonics, styling creams or gels or treatments packs,    -   oral care preparations such as pastes, gels, powders, mouth        washes and sprays.

A preferred embodiment is a personal care composition, comprising

-   A) at least one polymeric, ionic compound comprising imidazolium    groups (imidazolium compound), obtainable by reacting    -   a) at least one α-dicarbonyl compound,    -   b) at least one aldehyde,    -   c) at least one amino compound having at least two primary amino        groups,    -   d) optionally an amino compound having only one primary amino        group and    -   e) at least one protic acid,    -   and optionally subjecting the reaction product to an anion        exchange,    -   where the main chain of the at least one compound comprising        imidazolium groups does not contain 1,4-bound benzene rings;        specifically does not contain benzene rings, and    -   where in the components a) and b) the aldehyde carbonyl groups        may also be present as hemiacetal or acetal and the ketone        carbonyl groups may also be present as hemiketal or ketal,-   C) optionally at least one cosmetically acceptable active    ingredient, and-   D) optionally at least one cosmetically acceptable auxiliary.

Preferably, the main chain of the at least one imidazolium compoundapart from the nitrogen atoms of the imidazolium groups does not containany quaternary nitrogen atoms that bear 4 residues that are differentfrom hydrogen, either.

With regard to suitable and preferred embodiments of component A),reference is made to the afore-mentioned general definition of theimidazolium compounds employed according to the invention. With regardto suitable and preferred embodiments of cosmetically acceptablecomponents C) and D), reference is made to the following generaldefinition of those components.

Some appropriate personal care compositions include deodorants,antiperspirants, skin care products for facial, foot, hand and wholebody uses, sun protection products, personal cleaning products, haircare products, feminine hygiene products, oral care products anddecorative cosmetics such as lipsticks, mascara, facial makeup cremesand rouge.

Suitable cosmetic compositions may exist in a wide variety of forms, forexample:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W        or PIT emulsion and all kinds of microemulsions,    -   in the form of a gel,    -   in the form of an oil, a cream, milk or lotion,    -   in the form of a powder, a lacquer, a tablet or make-up,    -   in the form of a stick,    -   in the form of a spray (spray with propellant gas or pump-action        spray) or an aerosol,    -   in the form of a foam, or    -   in the form of a paste.

The cosmetic compositions may be, for example, creams, gels, lotions,alcoholic and aqueous/alcoholic solutions, emulsions, wax/fatcompositions, stick preparations, powders or ointments.

As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/Wemulsions or microemulsions) the preparations contain, for example, from0.1 to 30% by weight, preferably from 0.1 to 15% by weight andespecially from 0.5 to 10% by weight, based on the total weight of thecomposition, of one or more UV absorbers, from 1 to 60% by weight,especially from 5 to 50% by weight and preferably from 10 to 35% byweight, based on the total weight of the composition, of at least oneoil component, from 0 to 30% by weight, especially from 1 to 30% byweight and preferably from 4 to 20% by weight, based on the total weightof the composition, of at least one emulsifier, from 10 to 90% byweight, especially from 30 to 90% by weight, based on the total weightof the composition, of water, and from 0 to 88.9% by weight, especiallyfrom 1 to 50% by weight, of further cosmetically acceptable adjuvants.

The cosmetic composition may also contain one or one more additionalcomponents C) and/or D), as described below.

Of special importance are cosmetic preparations for the hair, especiallywith the purpose of antidandruff treatment are the above-mentionedpreparations for hair treatment, especially hair-washing preparations inthe form of shampoos, hair conditioners, hair-care preparations, e.g.pre-treatment preparations, hair tonics, styling creams, styling gels,pomades, hair rinses, treatment packs, intensive hair treatments,hair-straightening preparations, liquid hair-setting preparations, hairfoams and hairsprays. Of special interest are hair-washing preparationsin the form of shampoos.

A shampoo has, for example, the following composition:

from 0.01 to 5% by weight of the at least one component A),12.0% by weight of sodium laureth-2-sulfate,4.0% by weight of cocamidopropyl betaine,3.0% by weight of sodium chloride, andwater ad 100%.

For example, especially the following hair-cosmetic formulations may beused:

-   a1) spontaneously emulsifying stock formulation, consisting of the    antibacterial composition according to the above disclosure,    PEG-6-C₁₀oxoalcohol and sorbitan sesquioleate, to which water and    any desired quaternary ammonium compound, for example 4%    minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or    Quaternium 80 is added;-   a2) spontaneously emulsifying stock formulation consisting of the    antibacterial composition according to the above disclosure,    tributyl citrate and PEG-20-sorbitan monooleate, to which water and    any desired quaternary ammonium compound, for example 4%    minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or    Quaternium 80 is added;-   b) quat-doped solutions of the antibacterial composition as    disclosed above in butyl triglycol and tributyl citrate;-   c) mixtures or solutions of the antibacterial composition as    disclosed above with n-alkylpyrrolidone.

As used herein “cosmetically acceptable medium” means a medium which isnon-toxic, non-irritating and otherwise suitable for contact with thesurfaces of a human or other vertebrate body. Such surfaces include thehair, skin, mouth, anal, urethral and vaginal surfaces. Whether acomposition is physiologically acceptable can be determined by testswell known to those of skill in the art.

A further aspect of the invention is a method of using the presentpersonal care composition. The methods include contacting the personalcare compositions with a part of the human body. In general, the methodcomprises applying the personal care composition to a body surface orpart to be treated.

The term “applying” includes an appropriate action on the part of theuser to contact the personal care composition to the body part. Applyingincludes, in some embodiments, spreading, spraying, squirting, wipingand brushing. The particular type of application depends on the bodypart to which the personal care composition is to be applied.

“Body part” means a part of body including the mouth and otherepithelial surfaces of the body. Thus the term body part includes hair,skin and mouth, anus, urethra and vagina. In the case of the skin, thebody part is often more specific. For example, in some embodiments thebody part is the skin of the face, hand or foot. In other embodiments,the body part is the whole body. In other embodiments, for example wherethe personal care compositions are deodorants or antiperspirants, bodypart can be the underarms.

Preferably, the cosmetic composition comprises the components A) and, ifpresent, B) in a fraction of from about 0.001 to 50% by weight,particularly preferably 0.01 to 30% by weight, in particular 0.05 to 20%by weight, based on the total weight of the composition.

Cosmetically Acceptable Components C) and D) (General Definition)

The components C) and D) of the cosmetic composition are preferablychosen from cosmetically acceptable carriers, emulsifiers, surfactants,perfume oils, rheology modifiers (thickeners), hair polymers, hair andskin conditioners, water-soluble or dispersible silicone-comprisingpolymers, bleachers, gelling agents, care agents, colorants, tintingagents, tanning agents, dyes, pigments, antidandruff agents, sunscreenagents, deodorizing active substances, vitamins, plant extracts, bodyingagents, humectants, refatting agents, collagen, protein hydrolysates,lipids, antioxidants, antifoaming agents, antistatic agents, emollients,softeners, etc.

A comprehensive description of cosmetic auxiliaries is found in H. P.Fiedler, Lexikon der Hilfsstoffe für Pharmazie, Kosmetik and angrenzendeGebiete [Encyclopedia of Auxiliaries for Pharmaceuticals, Cosmetics andRelated Fields], 4th edition, Aulendorff: ECV-Editio-Cantor-Verlag,1996. A comprehensive description of cosmetic raw materials, auxiliariesand active substances, and also suitable formulations, are additionallyfound in K. Schrader, Grundlagen and Rezepturen der Kosmetika[Fundamental Principles and Formulations of Cosmetics], 2nd edition,Hüthig-Verlag, Heidelberg (1989).

A cosmetically acceptable medium comprises at least one cosmeticallyacceptable carrier. The cosmetic compositions preferably have a carriercomponent D) which is chosen from water, hydrophilic components,hydrophobic components and mixtures thereof.

Suitable hydrophilic carriers D) are, for example, mono-, di- orpolyhydric alcohols having preferably 1 to 8 carbon atoms, such asethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol,etc.

Suitable hydrophobic carriers D) are preferably chosen from

i) oils, fats, waxes,ii) esters of C₆-C₃₀-monocarboxylic acids with mono-, di- or trihydricalcohols which are different from iii),iii) saturated acyclic and cyclic hydrocarbons,iv) fatty acids,v) fatty alcohols,vi) propellant gases,and mixtures thereof.

Suitable silicone oils D) are volatile and non-volatile silicone oils.The term “volatile oil” means an oil capable of evaporating from theskin or the lips in less than one hour, and especially having a vaporpressure, at room temperature and atmospheric pressure, ranging from10⁻³ to 300 mm Hg (0.13 Pa to 40,000 Pa).

Suitable silicone oils D) are for example, linear polydimethylsiloxanes,poly(methylphenylsiloxanes), optionally substituted with aliphaticand/or aromatic groups, which are optionally fluorinated, or withfunctional groups, such as hydroxyl, thiol and/or amine groups. Suitablesilicone oils D) are also cyclic siloxanes. The number-average molecularweight of the polydimethylsiloxanes and poly(methylphenylsiloxanes) ispreferably in a range from about 1000 to 150 000 g/mol. Preferred cyclicsiloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes arecommercially available, for example, under the name cyclomethicone.

As volatile silicone oils that may be used in the invention, mention maybe made of linear or cyclic silicones containing from 2 to 7 siliconatoms, these silicones optionally comprising alkyl or alkoxy groupscontaining from 1 to 10 carbon atoms. Mention may be made in particularof octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,heptamethyloctyltrisiloxane, octamethyltrisiloxane anddecamethyltetrasiloxane, and mixtures thereof. Among the non-volatilesilicone oils that may be mentioned are non-volatilepolydialkylsiloxanes, such as non-volatile polydimethylsiloxanes (PDMS);polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, whichare pendent or at the end of a silicone chain, these groups containingfrom 2 to 24 carbon atoms; phenyl silicones, for instance phenyltrimethicones, phenyl dimethicones, phenyl trimethyl-siloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes and polymethylphenylsiloxanes; polysiloxanesmodified with fatty acids (especially of C₈-C₂₀), fatty alcohols(especially of C₈-C₂₀) or polyoxyalkylenes (especially polyoxy-ethyleneand/or polyoxypropylene); amino polysiloxanes; polysiloxanes containinghydroxyl groups; fluoro poly-siloxanes comprising a fluorinated groupthat is pendent or at the end of a silicone chain, containing from 1 to12 carbon atoms, all or some of the hydrogen atoms of which are replacedwith fluorine atoms; and mixtures thereof.

Preferred oil and fat components D) are chosen from paraffin andparaffin oils; vaseline; natural fats and oils, such as castor oil, soyaoil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil,cocoa butter, almond oil, peach kernel oil, ricinus oil, cod-liver oil,pig fat, spermaceti, spermaceti oil, sperm oil, wheatgerm oil, macadamianut oil, evening primrose oil, jojoba oil; fatty alcohols, such aslauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleylalcohol, cetyl alcohol; fatty acids, such as myristic acid, stearicacid, palmitic acid, oleic acid, linoleic acid, linolenic acid andsaturated, unsaturated and substituted fatty acids different therefrom;waxes, such as beeswax, carnauba wax, candililla wax, spermaceti, andmixtures of the abovementioned oil and fat components.

Suitable cosmetically and pharmaceutically compatible oil and fatcomponents D) are described in Karl-Heinz Schrader, Grundlagen andRezepturen der Kosmetika [Fundamentals and formulations of cosmetics],2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, which is herebyincorporated by reference.

Suitable cosmetically active substances C) are, for example, skin andhair pigmentation agents, tanning agents, bleaches, keratin-hardeningsubstances, antimicrobial active substances, photofilter activesubstances, repellent active substances, hyperemic substances,keratolytic and keratoplastic substances, antidandruff activesubstances, antiphlogistics, keratinizing substances, active substanceswhich act as antioxidants and/or as free-radical scavengers, skinmoisturizing or humectant substances, refatting active substances,deodorizing active substances, sebostatic active substances, plantextracts, antierythimatous or antiallergic active substances andmixtures thereof.

Artificially skin-tanning active substances C) which are suitable fortanning the skin without natural or artificial irradiation with UV raysare, for example, dihydroxyacetone, alloxan and walnut shell extract.Suitable keratin-hardening substances are generally active substances asare also used in antiperspirants, such as, for example, potassiumaluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.Antimicrobial active substances are used in order to destroymicroorganisms and/or to inhibit their growth and thus serve both aspreservatives and also as deodorizing substance which reduces theformation or the intensity of body odor. These include, for example,customary preservatives known to the person skilled in the art, such asp-hydroxybenzoates, imidazolidinylurea, formaldehyde, sorbic acid,benzoic acid, salicylic acid, etc. Such deodorizing substances are, forexample, zinc ricinoleate, triclosan, undecylenic acid alkylolamides,triethyl citrate, chlorhexidine etc. Suitable photofilter activesubstances are substances which absorb UV rays in the UV-B and/or UV-Aregion. Suitable UV filters are those specified above. Also suitable arep-aminobenzoic esters, cinnamic esters, benzophenones, camphorderivatives, and pigments which stop UV rays, such as titanium dioxide,talc and zinc oxide. Suitable repellent active substances are compoundswhich are able to keep or drive certain animals, in particular insects,away from people. These include, for example, 2-ethyl-1,3-hexanediol,N,N-diethyl-m-toluamide, etc. Suitable hyperemic substances whichstimulate blood flow in the skin are, for example, essential oils, suchas dwarf-pine, lavender, rosemary, juniper berry, horse chestnutextract, birch leaf extract, hay flower extract, ethyl acetate, camphor,menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitablekeratolytic and keratoplastic substances are, for example, salicylicacid, calcium thioglycolate, thioglycolic acid and its salts, sulfur,etc. Suitable antidandruff active substances are, for example, sulfur,sulfur polyethylene glycol sorbitan monooleate, sulfur ricinolpolyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitableantiphlogistics, which counteract skin irritations, are, for example,allantoin, bisabolol, dragosantol, camomile extract, panthenol, etc.

The compositions according to the invention can comprise, as activesubstance C) at least one polymer. These include, very generally,anionic, cationic, amphoteric and neutral polymers.

Suitable anionic polymers C) for the personal care compositionsaccording to the invention are generally all anionic polymers known forthis application. The composition according to the invention preferablycomprises at least one soluble or dispersed anionic polymer. The anionicpolymers that may be employed include, but are not limited to, polymerscomprising groups derived from carboxylic acids, sulfonic acids orphosphoric acids. Preferably, the anionic polymers have a number-averagemolecular mass in a range from 500 to 5 000 000.

The anionic polymers C) used in the personal care compositions accordingto the invention are preferably selected from:

A) Homo- or copolymers of acrylic or methacrylic acid or salts thereof.Examples are the products sold under the names VERSICOL® E or K by thecompany Allied Colloid and ULTRAHOLD® by BASF SE. Further preferredanionic polymers C) are the copolymers of acrylic acid and acrylamideand salts thereof. Examples are the products sold in the form of theirsodium salt under the names RETEN® 421, 423 or 425 by the companyHercules. Further preferred anionic polymers C) are the sodium salts ofpolyhydroxycarboxylic acids;B) Copolymers of acrylic or methacrylic acids with a monoethylenicmonomer, such as ethylene, styrene, vinyl esters and acrylic ormethacrylic acid esters, optionally grafted onto a polyalkylene glycol,such as polyethylene glycol and optionally crosslinked. Such polymersare described, for example, in French patent 1 222 944 and German patentapplication No. 2 330 956. Suitable are also copolymers whose polymerchain comprises acrylamide units that are optionally N-alkylated and/orhydroxyalkylated. Examples are the polymers described, e.g. in theLuxembourg patent applications 75370 and 75371 or sold under the nameQUADRAMER® by the company American Cyanamid. Suitable are alsocopolymers of acrylic acid and at least one (C₁-C₄)alkyl methacrylate,the copolymer of methacrylic acid and ethyl acrylate sold under the nameLUVIMER® MAE® by BASF SE; the terpolymer of tert-butyl acrylate, ethylacrylate and methacrylic acid sold under the name LUVIMER® 100 PLUVIMER® 36 D and LUVIMER® 30 E by BASF SE, the copolymer ofN-tert.-butylacrylamide, ethyl acrylate, acrylic acid (Ultraholdstrong);C) Copolymers derived from crotonic acid, such as those whose chaincomprises vinyl acetate or propionate units and optionally othermonomers, such as allylic or methallylic esters, vinyl ether or vinylester of a saturated, linear or branched carboxylic acid comprising along hydrocarbon-based chain, such as those comprising at least 5 carbonatoms, it being possible for these polymers to be grafted and/orcrosslinked, or alternatively a vinyl, allylic or methallylic ester ofan [alpha]- or [beta]-cyclic carboxylic acid. Preferred copolymers ofvinyl acetate, crotonic acid and optionally at least one further vinylester are the Luviset® trademarks of BASF SE. Such polymers are alsodescribed, inter alia, in French patents 1 222 944, 1 580 545, 2 265782, 2 265 781, 1 564 110 and 2 439 798. Further commercial productsfalling within this category are the resins 28-29-30, 26-13-14 and28-13-10 sold by National Starch;D) Polymers derived from maleic, fumaric or itaconic acids or anhydrideswith vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivativesor acrylic acid and its esters. The polymers of this category may beesterified. Such polymers are described e.g. in U.S. Pat. Nos.2,047,398, 2,723,248, and 2,102,113 and GB patent 839 805. Suitablecommercially available products are e.g. polymers sold under the namesGANTREZ® AN or ES by the company ISP. Polymers also falling within thiscategory are the copolymers of maleic, citraconic or itaconic anhydridesand of an allylic or methallylic ester optionally comprising anacrylamide or methacrylamide group, an [alpha]-olefin, acrylic ormethacrylic esters, acrylic or methacrylic acid or vinylpyrrolidone intheir chain, the anhydride functions being monoesterified ormonoamidated. These polymers are described, for example, in Frenchpatents 2 350 384 and 2 357 241 by the applicant;E) Polyacrylamides comprising carboxylate groups;F) Polymers comprising sulfonic groups are polymers comprisingvinylsulfonic, styrenesulfonic, naphthalenesulfonic oracrylamidoalkylsulfonic units. These polymers can be chosen, forexample, from: polyvinylsulfonic acid salts with a molecular weight in arange from 1000 to 100 000, and also copolymers with an unsaturatedcomonomer, such as acrylic or methacrylic acids and esters thereof, andalso acrylamide or derivatives thereof, vinyl ethers andvinylpyrrolidone; polystyrenesulfonic acid salts, the sodium saltshaving a molecular weight in a range from 500 000 to 100 000, sold,respectively, under the names FLEXAN® 500 and FLEXAN® 130 by NationalStarch. These compounds are described in patent FR 2 198 719; andpolyacrylamidesulfonic acid salts, such as those mentioned in U.S. Pat.No. 4,128,631 and, for example, polyacrylamidoethylpropanesulfonic acidsold under the name COSMEDIA POLYMER® HSP 1180 by Henkel.

Preferred examples of anionic polymers C) are homopolymers andcopolymers of acrylic acid and methacrylic acid or salts thereof,copolymers of acrylic acid and acrylamide and salts thereof; sodiumsalts of polyhydroxycarboxylic acids, water-soluble or water-dispersiblepolyesters, polyurethanes, e.g. Luviset PUR® from BASF, and polyureas.Particularly suitable polymers are copolymers of t-butyl acrylate, ethylacrylate, methacrylic acid (e.g. Luvimer® 100P), copolymers of ethylacrylate and methacrylic acid (e.g. Luvimer® MAE), copolymers ofN-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8,strong), copolymers of vinyl acetate, crotonic acid and if appropriatefurther vinyl esters (e.g. Luviset® grades), maleic anhydridecopolymers, if appropriate reacted with alcohol, anionic polysiloxanes,e.g. carboxyfunctional ones, t-butyl acrylate, methacrylic acid (e.g.Luviskol® VBM), copolymers of acrylic acid and methacrylic acid withhydrophobic monomers, such as, for example, C₄-C₃₀-alkyl esters of(meth)acrylic acid, C₄-C₃₀-alkylvinyl esters, C₄-C₃₀-alkyl vinyl ethersand hyaluronic acid. Examples of anionic polymers are also vinylacetate/crotonic acid copolymers, as are sold, for example, under thenames Resyn® (National Starch) and Gafset® (GAF), andvinylpyrrolidone/vinyl acrylate copolymers obtainable, for example,under the trade name Luviflex® (BASF). Further suitable polymers are thevinylpyrrolidone/acrylate terpolymer obtainable under the name Luviflex®VBM-35 (BASF) and polyamides containing sodium sulfonate or polyesterscontaining sodium sulfonate. Also suitable are vinylpyrrolidone/ethylmethacrylate/methacrylic acid copolymers, as are sold by Stepan underthe names Stepanhold-Extra and -R1, and the Carboset® grades from BFGoodrich. A further preferred example of an anionic polymer C) is amethyl methacrylate/methacrylic acid/acrylic acid/urethane acrylatecopolymer. Those polymers are commercially available as Luviset Shape®(INCI Name: Polyacrylate-22) from BASF SE. Luviset Shape is designede.g. for aqueous hair sprays to provide a fast-drying, non-tacky,long-lasting hold.

Suitable cationic polymers C) are polymers different from theimidazolium compounds according to the invention (=component A). Thecationic polymer C) may be chosen in principle from all cationicpolymers known to a person skilled in the art as suitable for cosmeticcompositions. Cationic polymers for compositions for improving thecosmetic properties of the hair are for example those described inpatent applications EP-A-0 337 354 FR-A-2 270 846, FR-2 383 660, FR-2598 611, FR-2 470 596 and FR-2 519 863. For the purposes of the presentinvention, the term “cationic polymer” denotes any polymer comprising atleast one cationic group or at least one cationogenic group that may beionized into a cationic group. The at least one cationic polymer may bechosen from those containing units comprising primary, secondary,tertiary, and/or quaternary amine groups that either may form part ofthe main polymer chain or may be borne by a side substituent directlyattached thereto.

Suitable cationic polymers C) are, for example:

(1) Homopolymers or copolymers derived from acrylic or methacrylicesters or amides and comprising at least one of the units of thefollowing formulae:

wherein:R3, which may be identical or different, is chosen from a hydrogen atomand a CH₃ radical;A, which may be identical or different, is chosen from linear orbranched alkyl groups comprising from 1 to 6 carbon atoms, for examplefrom 2 to 3 carbon atoms, and hydroxyalkyl groups comprising from 1 to 4carbon atoms;R₄, R₅ and R₆, which may be identical or different, are chosen fromalkyl groups comprising from 1 to 18 carbon atoms and a benzyl radical,and in at least one embodiment, R₄, R₅ and R₆, which may be identical ordifferent, are chosen from alkyl groups comprising from 1 to 6 carbonatoms;R₁ and R2, which may be identical or different, are chosen from hydrogenand alkyl groups comprising from 1 to 6 carbon atoms, for example methylor ethyl; andX⁻ is chosen from anions derived from a mineral or organic acid, such asa methosulfate anion, and halides, such as chloride or bromide.

The copolymers of group (1) may also comprise at least one unit derivedfrom comonomers that may be chosen from the family of acrylamides,methacrylamides, diacetone acrylamides, acrylamides, and methacrylamidessubstituted on the nitrogen with lower (C₁-C₄)alkyls, acrylic ormethacrylic acids or esters thereof, vinyllactams, such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Suitable members of group (1) are:

Copolymers of acrylamide and of dimethylaminoethyl methacrylatequaternized with dimethyl sulfate or with a dimethyl halide,the copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride described, for example,in EP-A-0 080 976,the copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium methosulfate,quaternized or nonquaternized vinylpyrrolidone/dialkylaminoalkylacrylate or methacrylate copolymers, such as those described in FRpatents 2 077 143 and 2 393 573,dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers,vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, andquaternized vinylpyrrolidone/dimethylaminopropylmethacrylamidecopolymers.

(2) Cationic polysaccharides, for example non-limiting mention may bemade of cationic celluloses and cationic galactomannan gums. In at leastone embodiment, the cationic polysaccharides are cellulose etherderivatives comprising quaternary ammonium groups, cationic cellulosecopolymers or cellulose derivatives grafted with a water-solublequaternary ammonium monomer and cationic galactomannan gums.

(3) Polymers comprising piperazinyl units and divalent alkylene orhydroxyalkylene radicals comprising straight or branched chains,optionally interrupted by oxygen, sulfur or nitrogen atoms or byaromatic or heterocyclic rings, and also the oxidation and/orquaternization products of these polymers.

(4) Water-soluble polyamino amides prepared, as non-limiting example, bypolycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, abis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkylhalide or alternatively with an oligomer resulting from the reaction ofa difunctional compound which is reactive with a bis-halohydrin, abis-azetidinium, a bis-haloacyidiamine, a bis-alkyl halide, anepihalohydrin, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in proportions ranging from 0.025 to 0.35mol per amine group of the polyamino amide; these polyamino amides canbe alkylated or, if they contain at least one tertiary amine function,they can be quaternized.

(5) Polyaminoamide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationwith difunctional agents. Non-limiting mention may be made, for example,of adipic acid/dialkylamino-hydroxyalkyldialkylenetriamine polymerswherein the alkyl radical comprises from 1 to 4 carbon atoms, such asmethyl, ethyl or propyl. Among these derivatives, non-limiting mentionmay be made of the adipicacid/dimethylaminohydroxypropyl/diethylenetriamine polymers.

(6) Polymers obtained by reaction of a polyalkylene polyamine comprisingtwo primary amine groups and at least one secondary amine group with adicarboxylic acid chosen from diglycolic acid and saturated aliphaticdicarboxylic acids comprising from 3 to 8 carbon atoms.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium,such as the homopolymers or copolymers comprising, as main constituentof the chain, units corresponding to formula

whereink and t are equal to 0 or 1, the sum k+t being equal to 1;R₁₂ is chosen from a hydrogen atom and a methyl radical;R₁₀ and R₁₁, which may be identical or different, are chosen from alkylgroups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups whereinthe alkyl group, for example, comprises from 1 to 5 carbon atoms, andlower (C₁-C₄)amidoalkyl groups, or R₁₀ and R₁₁, together with thenitrogen atom to which they are attached, are chosen from heterocyclicgroups such as piperidyl or morpholinyl; andY⁻ is an anion such as bromide, chloride, acetate, borate, citrate,tartrate, bisulfate, bisulfite, sulfate or phosphate.

Such polymers (7) are described, for example, in FR patent 2 080 759 andin its Certificate of Addition 2 190 406.

In at least one embodiment, R₁₀ and R₁₁, which may be identical ordifferent, are chosen from alkyl groups comprising from 1 to 4 carbonatoms.

Among the polymers defined above, non-limiting mention may be made, forexample, of the dimethyldiallylammonium chloride homopolymers sold underthe name MERQUAT® 100 by the company Nalco (and its homologs of lowweight-average molar mass) and copolymers of diallyldimethylammoniumchloride and of acrylamide.

(8) Quaternary diammonium polymers containing repeating unitscorresponding to the formula (6):

wherein:R₁₃, R₁₄, R₁₅ and R₁₆, which may be identical or different, are chosenfrom aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to20 carbon atoms, and lower hydroxyalkylaliphatic radicals such ashydroxyethyl, or R₁₃, R₁₄, R₁₅ and R₁₆, together or separately,constitute, with the nitrogen atoms to which they are attached,heterocycles optionally comprising a second heteroatom other thannitrogen, or R₁₃, R₁₄, R₁₅ and R₁₆ are chosen from a linear or branched(C₁-C₆)alkyl radical substituted with a nitrile, ester, acyl, or amidegroup, and a group —CO—O—R₁₇-D or —CO—NH—R₁₇-D, wherein R₁₇ is analkylene and D is a quaternary ammonium group;A₁ and B₁ are chosen from polymethylene groups comprising from 2 to 20carbon atoms, wherein the polymethylene groups may be linear orbranched, saturated or unsaturated, and wherein the polymethylene groupsmay comprise, linked to or intercalated in the main chain, at least onearomatic ring, at least one oxygen or sulfur atom, or sulfoxide,sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium,ureido, amide or ester groups, andX⁻ is an anion derived from a mineral or organic acid;or A₁, R₁₃ and R₁₅ can form, with the two nitrogen atoms to which theyare attached, a piperazine ring;in addition, if A₁ is chosen from a linear or branched, saturated orunsaturated alkylene or hydroxyalkylene radical, B₁ is chosen frompolymethylene groups comprising from 2 to 20 carbon atoms, wherein thepolymethylene groups may be linear or branched, saturated orunsaturated, and wherein the polymethylene groups may comprise, linkedto or intercalated in the main chain, at least one aromatic ring, atleast one oxygen or sulfur atom, sulfoxide, sulfone, disulfide, amino,alkylamino, hydroxyl, quaternary ammonium, ureido, amide or estergroups, and a group (CH₂)_(n)—CO-D-OC—(CH₂)_(n)—;wherein D is chosen from:a) a glycol residue of formula: —O—Z—O—, wherein Z is chosen from alinear or branched hydrocarbon-based radical, and a group correspondingto one of the following formulae:

—(CH₂—CH₂—O)_(x)—CH₂—CH₂— or —[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—

wherein x and y are integers ranging from 1 to 4, which is a defined andunique degree of polymerization or an average degree of polymerization;b) a bis-secondary diamine residue, such as a piperazine derivative;c) a bis-primary diamine residue of formula: —NH—Y—NH—, wherein Y ischosen from a linear or branched hydrocarbon-based-radical, and thedivalent radical

—CH₂—CH₂—S—S—CH₂—CH₂—; and

d) a ureylene group of formula: —NH—CO—NH—; andn is an integer ranging from 1 to 20, for example from 1 to 10.

In at least one embodiment, X⁻ is an anion such as chloride or bromide.

These polymers can have a number-average molar mass in a range from 1000to 100 000.

In at least one embodiment, polymers that consist of repeating unitscorresponding to formula (a) are used:

whereinR₁, R₂, R₃ and R₄, which may be identical or different, are chosen fromalkyl and hydroxyalkyl radicals comprising from 1 to 4 carbon atoms, nand p are integers ranging from 2 to 20, and X⁻ is an anion derived froma mineral or organic acid.

In at least one embodiment, R₁, R₂, R₃ and R₄ are chosen from a methylradical and n=3, p=6 and X=Cl. Such a polymer is known as hexadimethrinechloride according to the INCI (CTFA) nomenclature.

(9) Polyquaternary ammonium polymers comprised of units of formula (7):

wherein:R₁₈, R₁₉, R₂₀ and R₂₁, which may be identical or different, are chosenfrom a hydrogen atom, and methyl, ethyl, propyl, [beta]-hydroxyethyl,[beta]-hydroxypropyl and —CH₂CH₂(OCH₂CH₂)_(p)OH radicals, wherein p isequal to 0 or to an integer ranging from 1 to 6, with the proviso thatR₁₈, R₁₉, R₂₀ and R₂₁ do not simultaneously represent a hydrogen atom,r and s, which may be identical or different, are integers ranging from1 to 6,q is an integer ranging from 1 to 34,X⁻ is an anion such as a halide,A is chosen from a dihalide radical and —CH₂—CH₂—O—CH₂—CH₂—. In at leastone embodiment, A is —CH₂—CH₂—O—CH₂—CH₂—.

Non-limiting examples of such compounds are described in patentapplication EP-A-122 324.

Non-limiting examples include the products MIRAPOL® A15, MIRAPOL® (R)AD1, MIRAPOL® AZ1 and MIRAPOL® 175 sold by the company Miranol.

(10) Quaternary polymers of vinyllactam (vinylpyrrolidone and/orvinylcaprolactam) and of vinylimidazole.

(11) Crosslinked polymers ofmethacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkyl-ammonium salts, such as thepolymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization ofacrylamide with dimethylaminoethyl methacrylate quaternized with methylchloride, the homo- or copolymerization being followed by crosslinkingwith a compound containing olefinic unsaturation, for examplemethylenebisacrylamide.

Other cationic polymers C) that can be used in the context of thedisclosure are cationic proteins or cationic protein hydrolysates,polyalkyleneimines, for example non-limiting mention may be made ofpolyethyleneimines, polymers containing vinylpyridine or vinylpyridiniumunits, condensates of polyamines and of epichlorohydrin, quaternarypolyureylenes and chitin derivatives.

Preferred cationic polymers C) are polymers with the INCI namePolyquaternium, e.g. copolymers of vinylpyrrolidone/N-vinylimidazoliumsalts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®,Luviquat Supreme®, Luviquat® Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and-10), acrylamido copolymers (Polyquaternium-7) and chitosan. Suitablecationic (quaternized) polymers are also Merquat® (polymer based ondimethyldiallylammonium chloride), Gafquat® (quaternary polymers whichare formed by reacting polyvinylpyrrolidone with quaternary ammoniumcompounds), Polymer JR (hydroxyethylcellulose with cationic groups) andcationic polymers based on plants, e.g. guar polymers, such as theJaguar® grades from Rhodia.

Suitable neutral polymers C) are e.g. polyvinylpyrrolidones, copolymersof N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate,polysiloxanes, polyvinylcaprolactam and other copolymers withN-vinylpyrrolidone, polyethyleneimines and salts thereof,polyvinylamines and salts thereof, cellulose derivatives, polyasparticacid salts and derivatives. These include, for example, Luviflex® Swing(partially saponified copolymer of polyvinyl acetate and polyethyleneglycol, BASF).

Suitable polymers C) are also nonionic, water-soluble orwater-dispersible polymers or oligomers, such as polyvinylcaprolactam,e.g. Luviskol® Plus (BASF), or polyvinylpyrrolidone and copolymersthereof, in particular with vinyl esters, such as vinyl acetate, e.g.Luviskol® VA 37 (BASF); polyamides, e.g. based on itaconic acid andaliphatic diamines, as are described, for example, in DE-A-43 33 238.

Suitable polymers C) are also amphoteric or zwitterionic polymers, suchas the octylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers obtainable underthe names Amphomer® (National Starch), and zwitterionic polymers, as aredisclosed, for example, in the German patent applications DE 39 29 973,DE 21 50 557, DE 28 17 369 and DE 37 08 451.Acrylamidopropyltrimethylammonium chloride/acrylic acid or methacrylicacid copolymers and alkali metal and ammonium salts thereof arepreferred zwitterionic polymers. Further suitable zwitterionic polymersare methacroylethylbetaine/methacrylate copolymers, which arecommercially available under the name Amersette® (AMERCHOL), andcopolymers of hydroxyethyl methacrylate, methyl methacrylate,N,N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).

Suitable polymers C) are also nonionic, anionic, cationic or amphotericsiloxane-containing, polymers. Suitable are in principle organomodifiedand non-organomodified silicones. Siloxane containing polymers aretypical cosmetically acceptable agents that are beneficial to keratinmaterial. The silicones that can be used in accordance with theinvention may be soluble or insoluble in the composition. They may be inthe form of oils, waxes, resins or gums. Non-limiting examples of theorganopolysiloxanes are defined in greater detail in Walter Noll's“Chemistry and Technology of Silicones” (1968) Academic Press. They canbe volatile or nonvolatile. With regard to volatile silicones, referenceis made to the volatile silicone oils mentioned above. Volatilesilicones are preferably chosen from those having a boiling point in arange from 60° C. to 260° C.

Examples of volatile silicones are:

(i) Cyclic silicones comprising from 3 to 7 and for example from 4 to 5silicon atoms. These are, for example, but not limited to,octamethylcyclotetrasiloxane sold under the name Volatile Silicone 7207by Union Carbide or SILBIONE® 70045 V 2 by Rhodia,decamethylcyclopentasiloxane sold under the name Volatile Silicone 7158by Union Carbide, and SILBIONE® 70045 V 5 by Rhodia, and mixturesthereof.

Suitable are also cyclocopolymers of thedimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone FZ3109 sold by the company Union Carbide, having the general chemicalstructure:

with

Suitable are also mixtures of cyclic silicones with organosiliconecompounds, such as the mixture of octamethylcyclotetrasiloxane andtetratrimethylsilylpentaerythritol (50/50) and the mixture ofoctamethylcyclotetrasiloxane andoxy-1,1′-bis(2,2,2′,2′,3,3′-hexa-trimethylsilyloxy)neopentane;

(ii) Linear volatile silicones comprising from 2 to 9 silicon atoms andhaving a viscosity of less than or equal to 5×10⁻⁶ m²/s at 25° C. Anon-limiting example is decamethyltetrasiloxane sold under the name SH200 by the company Toray Silicone. Silicones belonging to this categoryare also described in Todd & Byers “Volatile Silicone Fluids forCosmetics”, Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32.

Further examples of nonvolatile silicones that are suitable as componentC) include polyalkylsiloxanes, polyarylsiloxanes,polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanesmodified with organofunctional groups, and also mixtures thereof.

Organomodified silicones that can be used in accordance with theinvention are silicones as defined above and comprising in theirstructure at least one organofunctional group attached via ahydrocarbon-based group.

Examples of organomodified silicones are polyorganosiloxanes comprising:

Polyethyleneoxy and/or polypropyleneoxy groups optionally comprising(C₆-C₂₄)alkyl groups. Such polyorganosiloxanes are commerciallyavailable, such as the products known as dimethicone copolyol sold bythe company Dow Corning under the name DC 1248, SILWET® L 722, L 7500, L77 and L 711 by the company Union Carbide, and the (C₁₂alkyl)methiconecopolyol sold by the company Dow Corning under the name Q2 5200;suitable nonionic siloxane-containing polymers C) are also polyethersiloxanes, such as the Tegopren® trademarks (Goldschmidt) or Belsil®trademarks (Wacker);substituted or unsubstituted amine groups. Such polyorganosiloxanes withsubstituted or unsubstituted amine groups are commercially available,such as the products sold under the name GP 4 Silicone Fluid and GP 7100by the company Genesee, or the products sold under the names Q2 8220 andDow Corning 929 or 939 by the company Dow Corning. The substituted aminegroups are, for example, (C₁-C₄)aminoalkyl groups;thiol groups. Such polyorganosiloxanes with thiol groups arecommercially available, e.g. the products sold under the names GP 72 Aand GP 71 from Genesee;alkoxylated groups. Such polyorganosiloxanes with alkoxylated groups arecommercially available, such as the product sold under the name SiliconeCopolymer F-755 by SWS Silicones and ABIL WAX® 2428, 2434 and 2440 bythe company Goldschmidt;hydroxylated groups. Such polyorganosiloxanes with alkoxylated groupsare commercially available, e.g. the polyorganosiloxanes comprising ahydroxyalkyl function, described in French patent applicationFR-A-85/16334;acyloxyalkyl groups. Such polyorganosiloxanes with acyloxyalkyl groupsare commercially available, e.g. the polyorganosiloxanes described inU.S. Pat. No. 4,957,732;anionic groups of the carboxylic acid type. Such polyorganosiloxaneswith anionic groups of the carboxylic acid type are commerciallyavailable, e.g. the products described in patent EP 186 507 from thecompany Chisso Corporation;anionic groups of the alkylcarboxylic type. Such polyorganosiloxaneswith anionic groups of the alkylcarboxylic type are commerciallyavailable, e.g. those present in the product X-22-3701E from the companyShin-Etsu;2-hydroxyalkyl sulfonate groups;2-hydroxyalkyl thiosulfate groups. Such polyorganosiloxanes with2-hydroxyalkyl thiosulfate are commercially available, e.g. such as theproducts sold by the company Goldschmidt under the names ABIL® S201 andABIL® S255; andhydroxyacylamino groups. Such polyorganosiloxanes with 2-hydroxyalkylthiosulfate are commercially available, e.g. the polyorganosiloxanesdescribed in patent application EP 342 834. Non-limiting mention may bemade, for example, of the product Q2-8413 from the company Dow Corning.

The personal care compositions according to the invention may compriseas component C) at least one polyisobutene or poly(α-olefin), chosenfrom those that are well known in the art. A preferred product isLuvitol Lite (INCI Name: Hydrogenated Polyisobutene) from BASF SE.Polyisobutenes and poly(α-olefins) can be used advantageously as a hairand skin conditioner. E.g. Luvitol Lite provides on the skin a pleasantsoft feeling without being oily. Polyisobutenes and poly(α-olefins) canalso be used as a conditioner in hair products, such as shampoos andbody washes, hair styling and conditioning applications. They contributeto properties, such as manageability, wet and dry comb, and shine.Finally, below is a simple example of Luvitol Lite's use in a shampootype formula with more than 60% oil, which, I suspect, does not foamvery much.

In addition to the abovementioned constituents, the personal carecompositions according to the invention can also comprise at least onesurface-active substance as component D). The surface-active substancesinclude surfactants, dispersing agents and wetting agents.

Suitable are anionic, cationic, nonionic and amphoteric surfactants,including polymer surfactants and surfactants with heteroatoms in thehydrophobic group.

The following list of suitable and preferred surfactants is not limitedto the application in personal care compositions but is applicable toall biocide compositions according to the invention.

Non-limiting examples of anionic surfactants useful in embodiments ofthe compositions of the present invention are disclosed in McCutcheon's,Detergents and Emulsifiers, North American edition (1990), published byThe Manufacturing Confectioner Publishing Co.; McCutcheon's, FunctionalMaterials, North American Edition (1992); and U.S. Pat. No. 3,929,678,to Laughlin et al., issued Dec. 30, 1975, all of which are incorporatedherein by reference.

Non-limiting examples of anionic surfactants useful in embodiments ofthe compositions of the present invention are disclosed in McCutcheon's,Detergents and Emulsifiers, North American edition (1990), published byThe Manufacturing Confectioner Publishing Co.; McCutcheon's, FunctionalMaterials, North American Edition (1992); and U.S. Pat. No. 3,929,678,to Laughlin et al., issued Dec. 30, 1975, all of which are incorporatedherein by reference.

Nonlimiting examples of anionic surfactants include alkyl and alkylether sulfates; sulfated monoglycerides; sulfonated olefins; alkyl arylsulfonates; primary or secondary alkane sulfonates; alkylsulfosuccinates; acyl taurates; acyl isethionates; alkyl glycerylethersulfonate; sulfonated methyl esters; sulfonated fatty acids; alkylphosphates; acyl glutamates; acyl sarcosinates; alkyl sulfoacetates;acylated peptides; alkyl ether carboxylates; acyl lactylates; anionicfluorosurfactants; and mixtures thereof. Mixtures of anionic surfactantscan be used effectively in some embodiments of the present disclosure.

Suitable anionic surfactants for use in personal care compositionsaccording to the invention include alkyl sulfates and alkyl ethersulfates. Suitable components have the general formulae R¹¹—O—SO₃-M andR¹¹—(CH₂H₄—O)_(x)—O—SO₃-M, wherein R¹¹ is a saturated or unsaturated,branched or unbranched alkyl group from about 8 to about 24 carbonatoms, x is 1 to 10, and M is a water-soluble cation such as ammonium,sodium, potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. The alkyl sulfates are typically made by the sulfationof monohydric alcohols (having from about 8 to about 24 carbon atoms)using sulfur trioxide or other known sulfation technique. The alkylether sulfates are typically made as condensation products of ethyleneoxide and monohydric alcohols (having from about 8 to about 24 carbonatoms) and then sulfated. These alcohols can be derived from fats, forexample, coconut oil or tallow, or can be synthetic. Specific examplesof alkyl sulfates which are useful in some embodiments of inventivecleanser compositions are sodium, ammonium, potassium, magnesium, or TEAsalts of lauryl or myristyl sulfate. Examples of alkyl ether sulfatesinclude ammonium, sodium, magnesium, or TEA laureth-3 sulfate.

Another suitable class of anionic surfactants are sulfatedmonoglycerides of the general formula R¹²—CO—O—CH₂—C(OH)H—CH₂—O—SO₃-M,wherein R¹² is a saturated or unsaturated, branched or unbranched alkylgroup from about 8 to about 24 carbon atoms, and M is a water-solublecation such as ammonium, sodium, potassium, magnesium, triethanolamine,diethanolamine and monoethanolamine. These are typically made by thereaction of glycerin with fatty acids (having from about 8 to about 24carbon atoms) to form a monoglyceride and the subsequent sulfation ofthis monoglyceride with sulfur trioxide. An example of a sulfatedmonoglyceride is sodium cocomonoglyceride sulfate.

Other suitable anionic surfactants include olefin sulfonates of thegeneral formula R¹³SO₃-M, wherein R¹³ is a mono-olefin having from about12 to about 24 carbon atoms, and M is a water-soluble cation, such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. These compounds can be produced by the sulfonationof -olefins by means of uncomplexed sulfur trioxide, followed byneutralization of the acid reaction mixture in conditions, such that anysulfones which have been formed in the reaction are hydrolyzed to givethe corresponding hydroxyalkanesulfonate. An example of a sulfonatedolefin is sodium C14/C16-olefin sulfonate.

Other suitable anionic surfactants are the linear alkylbenzenesulfonates of the general formula R¹⁴—C₆H₄—SO₃-M, wherein R¹⁴ is asaturated or unsaturated, branched or unbranched alkyl group from about8 to about 24 carbon atoms, and M is a water-soluble cation such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. These are formed by the sulfonation of linearalkyl benzene with sulfur trioxide. An example of this anionicsurfactant is sodium dodecylbenzene sulfonate.

Further suitable anionic surfactants (in particular for the cleansingcompositions) include primary or secondary alkane sulfonates of the formR¹⁵—SO₃-M, wherein R¹⁵ is a saturated or unsaturated, branched orunbranched alkyl chain from about 8 to about 24 carbon atoms, and M is awater-soluble cation such as ammonium, sodium, potassium, magnesium,triethanolamine, diethanolamine and monoethanolamine. These are commonlyformed by the sulfonation of paraffins using sulfur dioxide in thepresence of chlorine and ultraviolet light or another known sulfonationmethod. The sulfonation can occur in either the secondary or primarypositions of the alkyl chain. An example of an alkane sulfonate usefulherein is alkali metal or ammonium C₁₃-C₁₇ paraffin sulfonates.

Further suitable anionic surfactants are alkyl sulfosuccinates, whichinclude disodium N-octadecylsulfosuccinamate; diammonium laurylsulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; diamyl ester of sodiumsulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; anddioctyl esters of sodium sulfosuccinic acid.

Also useful are taurates which are based on taurine, which is also knownas 2-aminoethanesulfonic acid. Examples of taurates includeN-alkyltaurines, such as the one prepared by reacting dodecylamine withsodium isethionate, according to the teaching of U.S. Pat. No. 2,658,072which is incorporated herein by reference in its entirety. Otherexamples of taurine derivatives that are useful in embodiments of thedisclosure include the acyl taurines formed by the reaction of n-methyltaurine with fatty acids (having from about 8 to about 24 carbon atoms).

Further suitable anionic surfactants are acyl isethionates. The acylisethionates typically have the formula R¹⁶—CO—O—CH₂—CH₂SO₃-M, whereinR¹⁶ is a saturated or unsaturated, branched or unbranched alkyl grouphaving from about 10 to about 30 carbon atoms, and M is a cation. Theseare typically formed by the reaction of fatty acids (having from about 8to about 30 carbon atoms) with an alkali metal isethionate. Nonlimitingexamples of these acyl isethionates include ammonium cocoyl isethionate,sodium cocoyl isethionate, sodium lauroyl isethionate, and mixturesthereof.

Further suitable anionic surfactants are alkylglyceryl ether sulfonatesof the form R¹⁷—OCH₂—C(OH)H—CH₂—SO₃-M, wherein R¹⁷ is a saturated orunsaturated, branched or unbranched alkyl group from about 8 to about 24carbon atoms, and M is a water-soluble cation, such as ammonium, sodium,potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. These can be formed by the reaction of epichlorohydrinand sodium bisulfite with fatty alcohols (having from about 8 to about24 carbon atoms) or other known methods. One example is sodiumcocoglyceryl ether sulfonate.

Further suitable anionic surfactants are sulfonated fatty acids of thegeneral formula R₁₈—CH(SO₄)—COOH and sulfonated methyl esters of thegeneral formula R¹⁸—CH(SO₄)—CO—O—CH₃, where R¹⁸ is a saturated orunsaturated, branched or unbranched alkyl group from about 8 to about 24carbon atoms. These surfactants are generally formed by the sulfonationof fatty acids or alkyl methyl esters (having from about 8 to about 24carbon atoms) with sulfur trioxide or by other known sulfonationtechniques. Examples include alpha sulfonated coconut fatty acid andlauryl methyl ester.

Further suitable anionic surfactants are phosphates, such as monoalkyl-,dialkyl-, and trialkylphosphate salts formed by the reaction ofphosphorous pentoxide with monohydric branched or unbranched alcoholshaving from about 8 to about 24 carbon atoms. In some embodiments, theseanionic materials are also be formed by other known phosphation methods.An example from this class of surfactants is sodium mono ordilaurylphosphate.

Further suitable anionic surfactants are acyl glutamates correspondingto the formula R¹⁹—CO—N(COOH)—CH₂CH₂—CO₂-M, wherein R¹⁹ is a saturatedor unsaturated, branched or unbranched alkyl or alkenyl group of about 8to about 24 carbon atoms, and M is a water 46 soluble cation.Nonlimiting examples of which include sodium lauroyl glutamate andsodium cocoyl glutamate.

Further suitable anionic surfactants are alkanoyl sarcosinatescorresponding to the formula R²⁰—CON(CH₃)—CH₂CH₂—CO₂-M, wherein R²⁰ is asaturated or unsaturated, branched or unbranched alkyl or alkenyl groupof about 10 to about 20 carbon atoms, and M is a watersoluble cation.Nonlimiting examples of which include sodium lauroyl sarcosinate, sodiumcocoyl sarcosinate, and ammonium lauroyl sarcosinate. Other anionicmaterials include alkyl ether carboxylates corresponding to the formulaR²¹—(OCH₂CH₂)_(x)—OCH₂—CO₂-M, wherein R²¹ is a saturated or unsaturated,branched or unbranched alkyl or alkenyl group of about 8 to about 24carbon atoms, x is 1 to 10, and M is a water-soluble cation. Nonlimitingexamples of which include sodium laureth carboxylate. Other anionicmaterials include acyl lactylates corresponding to the formulaR²²—CO—[O—CH(CH₃)—CO]_(x)—CO₂-M, wherein R²² is a saturated orunsaturated, branched or unbranched alkyl or alkenyl group of about 8 toabout 24 carbon atoms, x is 3, and M is a water-soluble cation,nonlimiting examples of which include sodium cocoyl lactylate. Otheranionic materials include the carboxylates, nonlimiting examples ofwhich include sodium lauroyl carboxylate, sodium cocoyl carboxylate, andammonium lauroyl carboxylate. Anionic fluorosurfactants can also beused. A counter cation, M, counterbalances the negative charge of theanionic surfactant. Some especially suitable counter cations are sodium,potassium, ammonium, monoethanolamine, diethanolamine, andtriethanolamine. An especially suitable counter cation is ammonium.

Suitable non-ionic surfactants for use in personal care compositionsaccording to the invention are condensation products of ethylene oxidewith various reactive hydrogen-containing compounds reactive therewithhaving long hydrophobic chains (for example aliphatic chains of about12-20 carbon atoms) which condensation products (“ethoxamers”) containhydrophilic polyoxyethylene moieties, such as condensation products ofpoly(ethyleneoxide) with fatty acids, fatty alcohols, fatty amides,polyhydric alcohols (for example sorbitan monostearate) andpolypropylene oxide (for example Pluronic a materials). Polyoxamersinclude for example block copolymers of polyoxyethylene andpolyoxypropylene having an average molecular weight from about 3000 to5000 and a preferred average molecular weight from about 3500 to 4000and containing about 10 to 80% hydrophilic polyoxyethylene groups, byweight, of the block copolymer (for example Pluronic F127). Othernon-ionic surfactants are for example alkyl polyglucosids,alcanolamides, ethers of e.g. fatty acids with ethylene oxid orpolyethylenglycol, amine oxids e.g. cocamidopropyla amine oxid.

Suitable amphoteric surfactants for use in personal care compositionsaccording to the invention are secondary or tertiary aliphatic aminederivatives, where the aliphatic chain can be linear or branched andcontains at least 8 to 22 carbon atoms and one anionic group, such ascarboxylate, sulfonate, sulfate, phosphate or phosphonate. Suitableamphoteric surfactants are also acyl/dialkyl ethylenediamines, such asacylamphoacetate, disodium acylamphodipropionate, sodiumacylamphohydroxypropylsulfonate, disodium acylamphodiacetate, sodiumacylamphopropionate, where acyl represents either an alkyl or alkenyl,mono- or polyunsaturated residue containing 5 to 29 carbon atoms.Suitable amphoteric surfactants are also N-alkyl amino acids or iminoacids, such as aminopropyl alkylglutamide, alkylaminopropionic acid,sodium alkylimino propionate, alkyl glycinates and carboxyglycinates,e.g. sodium cocoglycinate. Suitable amphoteric surfactants are alsoC₈-C₁₈-betains, C₈-C₁₈-sulfobetains, C₈-C₂₄-alkylamido-C₁-C₄-alkylenebetains, imidazoline carboxylates, alkylamphocarboxycarbonic acids,alkylamphocarbonic acid (for example lauroamphoglycinate) andN-alkyl-β-aminopropionate or N-alkyl-β-iminodi-propionate. Preferably,the amphoteric surfactant comprisesC₁₀-C₂₀-alkylamido-C₁-C₄-alkylenbetaine and/or coco fatty acid amidepropylbetaine.

Suitable thickening polymers useful herein as rheology modifier D)include anionic polymers, cationic polymers, amphoteric polymers andnonionic polymers. The thickening polymers useful herein include, forexample, acrylic polymers, polyalkylene glycol polymers having amolecular weight of more than about 10 000, celluloses and derivativesthereof, such as hydroxyethyl cellulose, polyvinylpyrrolidone, polyvinylalcohol, gums, such as guar gum and xanthan gum, carragenan, pectin,agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato,wheat), algae colloids (algae extract), dextran, succinoglucan,pulleran, carboxymethyl starch, methylhydroxypropyl starch, sodiumalginate, and alginic acid propylene glycol esters. Neutralizing agentsmay be included to neutralize the anionic thickening agents describedhereinabove. Nonlimiting examples of such neutralizing agents includesodium hydroxide, potassium hydroxide, ammonium hydroxide,monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine,aminomethylpropanol, trimethamine, tetrahydroxypropyl ethylenediamine,and mixtures thereof.

Preferred thickening polymers useful herein as rheology modifier D)include acrylic polymers. Acrylic polymers useful herein include thosecomprising monomers selected from the group consisting of acrylic acid,salts of acrylic acid, derivatives of acrylic acid, methacrylic acid,salts of methacrylic acid, derivatives of methacrylic acid, and mixturesthereof. The derivatives include, for example, alkyl acrylate,acrylamide, alkyl methacrylate, and methacrylamide. Such acrylicpolymers include, for example, cross linked acrylic acid polymers withthe CTFA name Carbomer, sodium polyacrylate, polyethylacrylate,polyacrylamide, and acrylic acid/alkyl acrylate copolymers with the CTFAname Acrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymer. Commerciallyavailable acrylic polymers highly useful herein include, for example,polyacrylamide with tradename Sepigel 305 available SEPPIC Inc., andAcrylates/C₁₀₋₃₀ Alkyl Acrylate Crosspolymer having tradenames PemulenTR-I, Pemulen TR-2, Carbopol 1342, Carbopol 1382, and Carbopol ETD 2020,all available from B.F. Goodrich Company.

Suitable thickening polymers useful herein as rheology modifier D)include also so called associative polymers. Suitable associativepolymers are mentioned in the following.

Preferred thickening polymers useful herein as rheology modifier D) arealso the following products that are commercially available from BASF SEand Cognis corporation:

Rheocare TTA (2-methyl-2-propenoic acid polymer with butyl 2-propenoateand ethyl 2-propenoate, CAS-No. 31069-81-5),LUVIGEL® grades, inter alia LUVIGEL® advance (cross-linked cationicrheology modifier), LUVIGEL® EM (milky emulsion of sodium acrylatescopolymer in caprylic/capric triglyceride and water) and LUVIGEL® STAR(non-ionic, electrolyte tolerant, polyurethane-based associativerheology modifier).

A cationic-compatible liquid rheology modifier that is especiallysuitable as component D) for the personal care compositions of theinvention is a cationic polymer with the INCI name polyacrylate-1crosspolymer. They are commercially available under the trade markCarbopol Aqua CC from Noveon Inc. The Polyacrylate-1 Crosspolymer is theproduct of the polymerization of a mixture of monomers comprising (orconstituted of):

-   -   a di(C₁-C₄ alkyl)amino(C₁-C₆ alkyl)methacrylate,    -   at least one (meth)acrylic acid C₁-C₃₀ alkyl ester,    -   a polyethoxylated C₁₀-C₃₀ alkyl methacrylate (20-25 mol of        ethylene oxide unit),    -   a polyethylene glycol/polypropylene glycol 30/5 alkyl ether,    -   a hydroxyl(C₂-C₆ alkyl)methacrylate, and    -   an ethylene glycol dimethacrylate.

The imidazolium compounds according to the invention can be employedadvantageously in detergent cosmetic compositions employed for cleansingand caring the hair or the skin.

A first special embodiment of the invention is a cosmetic composition,comprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A),    -   at least one surfactant and    -   at least one cosmetically acceptable active ingredient that is        beneficial to keratin materials.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. The at leastone imidazolium compound (=component A) may be used in combination withat least one further cationic polymer different from the compounds ofcomponent (A). With regard to suitable and preferred additional cationicpolymers, reference is made to the cationic polymers mentioned before ascomponent C).

With regard to suitable and preferred surfactants, reference is made tothe surfactants mentioned before as component D). Suitable surfactantsand in particular combinations of surfactants are disclosed in US2009/0048132 A1 which is incorporated herein by reference.

The at least one cosmetically acceptable active ingredient that isbeneficial to keratin materials is preferably selected from:

(1) hydrolyzed or nonhydrolyzed, modified or unmodified saccharides,oligosaccharides and polysaccharides,(2) hydrolyzed or nonhydrolyzed, modified or unmodified amino acids,oligopeptides, peptides and proteins,(3) branched or unbranched fatty acids and alcohols,(4) animal, plant and mineral waxes,(5) ceramides and pseudoceramides,(6) hydroxylated organic acids,(7) UV-screening agents,(8) antioxidants and free-radical scavengers,(9) chelating agents,(10) antidandruff agents,(11) seborrhea regulators,(12) calmatives,(13) cationic surfactants,(14) organomodified and non-organomodified silicones,(15) mineral, plant and animal oils,(16) polyisobutenes and poly([alpha]-olefins),(17) fatty esters, for example those comprising from 15 to 50 carbonatoms,(18) soluble and dispersed anionic polymers, and(19) soluble and dispersed nonionic polymers, and mixtures thereof.

Suitable compounds (1)-(19) are described in US 2009048132 A1 which isincorporated herein by reference.

A second special embodiment of the invention is a cosmetic compositioncomprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), and    -   at least one associative polymer.

Preferably, the composition according to the second special embodimentfurther comprises at least one surfactant. With regard to suitable andpreferred surfactants, reference is made to the surfactants mentionedbefore as component D).

Preferably, the composition according to the second special embodimentfurther comprises at least one conditioning agent. Preferably, the atleast one conditioning agent is chosen from silicones, cationic polymersother than the imidazolium compounds of the present disclosure, mineral,plant, and animal oils, ceramides, pseudoceramides, poly-α-olefins,fluoro oils, fluoro waxes, fluoro gums, carboxylic acid esters, etc.Preferably, the at least one conditioning agent is present in an amountranging from 0.001% to 20% by weight, more preferably 0.01% to 10% byweight, based the total weight of the composition. In particular, theconditioner is a rinse-out or leave-in conditioner.

Preferably, the composition according to the second special embodimentis in the form of a foaming detergent composition or a conditioner. Inparticular, the foaming detergent composition is a shampoo, shower gel,makeup-removing product, or bubble bath.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. The at leastone imidazolium compound (=component A) may be used in combination withat least one further cationic polymer different from the compounds ofcomponent (A). With regard to suitable and preferred additional cationicpolymers, reference is made to the cationic polymers mentioned before ascomponent C).

With regard to suitable and preferred associative polymers, reference ismade to WO 2010/023411 A2 which is incorporated herein by reference.Suitable cationic associative polymers and anionic associative polymersare also disclosed in US 2009/0074692 A1 which is incorporated herein byreference. Preferred associative polymers can be obtained bypolymerization of a monomer mixture comprising at least one associativevinyl monomer. Non-limiting examples of the at least one include(meth)acrylates of polyalkoxylated C₈-C₃₀ fatty alcohols and mixturesthereof. Preferred associative vinyl monomers are polyethoxylated cetyl(meth)acrylates, polyethoxylated cetearyl (meth)acrylates,polyethoxylated stearyl (meth)acrylates, polyethoxylated arachidyl(meth)acrylates, polyethoxylated behenyl (meth)acrylates, andpolyethoxylated lauryl (meth)acrylates. The polyalkoxylated portion ofthe associative monomer comprises preferably from 10 to 80, such as from15 to 40, and such as from 20 to 35 alkylene oxide units, selected fromethylene oxide, propylene oxide and mixtures thereof. Preferably, thepolyalkoxylated portion of the associative monomer comprises from 10 to80, more preferably from 15 to 40, and in particular from 20 to 35ethylene oxide units.

In a preferred embodiment, the at least one associative polymer isselected from anionic associative polymers. Preferably, the compositioncomprises the at least associative polymer in an amount of from 1 to 50wt %, more preferably of from 2 to 25 wt %, based on the total weight ofthe composition.

A third special embodiment is an antidandruff composition, comprising ina cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), and    -   optionally at least one antidandruff agent different from the        imidazolium compound.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. The at leastone imidazolium compound (=component A) may be used in combination withat least one further cationic polymer different from the compounds ofcomponent (A). With regard to suitable and preferred additional cationicpolymers, reference is made to the cationic polymers mentioned before ascomponent C).

Preferably, the composition according to the third special embodimentfurther comprises at least one surfactant. With regard to suitable andpreferred surfactants, reference is made to the surfactants mentionedbefore as component D). The surfactant is generally present in thecomposition according to the third special embodiment in an amountranging from 0.1% to 60% by weight approximately, preferably from 3% to40% and even more preferably from 5% to 30%, relative to the totalweight of the composition.

The antidandruff agent which is different from the imidazolium compoundsare chosen in particular from:

-   1) Pyridinethione salts, in particular the calcium, magnesium,    barium, strontium, zinc, cadmium, tin and zirconium salts. The zinc    salt of pyridinethione is particularly preferred. The zinc salt of    pyridinethione is sold in particular under the name ZINC OMADINE by    the company OLIN.-   2) 1-Hydroxy-2-pyrrolidone derivatives represented by formula (IV):

-   -   wherein:    -   R₉ is chosen from an alkyl group containing from 1 to 17 carbon        atoms, an alkenyl group containing from 2 to 17 carbon atoms, a        cycloalkyl group containing from 5 to 8 carbon atoms, a        bicycloalkyl group containing from 7 to 9 carbon atoms, a        cycloalkyl(alkyl) group, an aryl group wherein the aryl may have        as possible substituents a halogen group, a nitro group, and a        cyano group, an aralkyl group wherein the alkyl contains from 1        to 4 carbon atoms, an arylalkenyl group wherein the alkenyl        contains from 2 to 4 carbon atoms, an aryloxyalkyl wherein the        alkyl contains from 1 to 4 carbon atoms, arylmercaptoalkyl group        wherein the alkyl contains from 1 to 4 carbon atoms, a        furylalkenyl group wherein the alkenyl contains from 2 to 4        carbon atoms or wherein the furyl contains from 2 to 4 carbon        atoms, an alkoxy group containing from 1 to 4 carbon atoms, a        nitro group, a cyano group and a halogen atom;    -   R₁₀ is chosen from a hydrogen atom, a (C₁-C₄) alkyl group, a        (C₂-C₄) alkenyl group, a halogen atom, a phenyl group, and a        benzyl group; and    -   X⁺ is chosen from a quaternized organic base, an alkali metal        ion, alkaline-earth metal ion, and an ammonium ion.

Compounds of formula (IV) are, for example,1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone,1-hydroxy-4,6-dimethyl-2-pyridone,1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone,1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone,1-hydroxy-4-methyl-6-(methylcyclohexyl)-2-pyridone,1-hydroxy-4-methyl-6-(2-bicyclo (2,2,1) heptyl)-2-pyridone,1-hydroxy-4-methyl-6-(4-methylphenyl)-2-pyridone,1-hydroxy-4-methyl-6-(1-(4-nitrophenoxy)butyl)-2-pyridone,1-hydroxy-4-methyl-6-(4-cyanophenoxymethyl)-2-pyridone,1-hydroxy-4-methyl-6-(phenyl-sulphonylmethyl)-2-pyridone or1-hydroxy-4-methyl-6-(4-bromobenzyl)-2-pyridone.

The compounds of formula (IV) can be used in the form of salts withorganic or inorganic bases. Examples of organic bases are, inparticular, alkanolamines of low molecular weight, such as ethanolamine,diethanolamine, N-ethylethanolamine, triethanolamine,diethylaminoethanol and 2-amino-2-methylpropanediol; non-volatile bases,such as ethylenediamine, hexamethylenediamine, cyclohexylamine,benzylamine and N-methylpiperazine; quaternary ammonium hydroxides, suchas trimethylbenzyl hydroxide; guanidine and its derivatives, and inparticular its alkyl derivatives. Examples of inorganic bases are, inparticular, alkali metal salts, such as sodium and potassium salts;ammonium salts, alkaline-earth metal, salts such as magnesium andcalcium salts; salts of divalent, trivalent or tetravalent cationicmetals, such as zinc, aluminium or zirconium. The alkanolamines,ethylenediamine and inorganic bases, such as the alkali metal salts arepreferred.

In a particularly preferred embodiment, in the compound of formula (IV)R₉ is a radical

R₁₀ is a methyl group, andX⁺ is N⁺H₃CH₂CH₂OH.

This compound (IV) is commercially available under the name OCTOPIROX(1-hydroxy4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone,monoethanolamine salt).

-   3) 2,2′-Dithiobis(pyridine N-oxide) of formula (V):

The compounds of formula (V) can be introduced into the composition inthe form of inorganic salts. An example of an inorganic salt ismagnesium sulphate.

-   4) Trihalocarbamides of formula (VI) below:

wherein:Z is a halogen atom, such as chlorine, or a (C₁-C₄) trihaloalkyl group,such as CF₃.

-   5) Triclosan, represented by formula (VII):

-   6) Azo compounds, such as climbazole, ketoconazole, clotrinazole,    econazole, isoconazole and miconazole;-   7) Antifungal polymers, such as amphotericin B or nystatin;-   8) Selenium sulphide;-   9) Other antidandruff agents are sulphur in its various forms,    cadmium sulphide, allantoin, coal tars or wood tars and derivatives    thereof, in particular cade oil, salicylic acid, undecylenic acid,    fumaric acid and allylamines, such as terbinafine.

Zinc Omadoine, Octopirox and selenium sulphide are particularlypreferred.

Preferably, the at least imidazolium compound and the additionalantidandruff agent(s) are present in an amount ranging from 0.01% to 10%by weight and more particularly from 0.1 to 5% by weight, based on thetotal weight of the composition.

A fourth special embodiment is a composition for the treatment of acneand cutaneous disorders linked to hyperseborrhoea, comprising in acosmetically acceptable medium at least one imidazolium compound(=component A).

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. Suitableformulations are disclosed in WO 03/000221 A1 which is incorporatedherein by reference.

A fifth special embodiment is a hair dye composition, comprising in acosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), and    -   at least one cationic dye.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. Suitable hairdye formulations are disclosed in FR 2912908 A1 which is incorporatedherein by reference. It was surprisingly found that advantageousproperties are obtained, if the cationic polymers used in the hair dyecompositions according to this document are replaced completely orpartly by at least one imidazolium compound employed according to theinvention.

A sixth special embodiment is a cosmetic composition for treating akeratinous substrate, comprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one fatty quaternary amine.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention.

The at least one fatty quaternary amine is preferably selected fromcompounds containing from about 6 to about 22 carbon atoms. The anion ofthe quaternary agent can be a common ion, such as chloride, ethosulfate,methosulfate, acetate, bromide, lactate, nitrate, phosphate, or tosylateand mixtures thereof. The long chain alkyl groups can include additionalor replaced carbon or hydrogen atoms or ether linkages. Othersubstitutions on the quaternary nitrogen can be hydrogen, benzyl orshort chain alkyl or hydroxyalkyl groups, such as methyl, ethyl,hydroxymethyl or hydroxyethyl, hydroxypropyl or combinations thereof.

Examples of fatty quaternary amines include, but are not limited to:Behentrimonium chloride, Cocotrimonium chloride, Cethethyldimoniumbromide, Dibehenyldimonium chloride, Dihydrogenated tallow benzylmoniumchloride, disoyadimonium chloride, Ditallowedimonium chloride,Hydroxycetyl hydroxyethyl dimonium chloride, HydroxyethylBehenamidopropyl dimonium chloride, Hydroxyethyl Cetyldimonium chloride,Hydroxyethyl tallowedimonium chloride, myristalkonium chloride, PEG-2Oleamonium chloride, PEG-5 Stearmonium chloride, PEG-15 cocoylquaternium 4, PEG-2 stearalkonium 4, lauryltrimonium chloride;Quaternium-16; Quaternium-18, lauralkonium chloride, olealkoniumchloride, cetylpyridinium chloride, Polyquaternium-5, Polyquaternium-6,Polyquaternium-7, Polyquaternium-10, Polyquaternium-22,Polyquaternium-37, Polyquaternium-39, Polyquaternium-47, cetyl trimoniumchloride, dilauryldimonium chloride, cetalkonium chloride,dicetyldimonium chloride, soyatrimonium chloride, stearyl octyl dimoniummethosulfate, behentrimonium methosulfate (18-MEA), stearalkoniumchloride, and mixtures thereof. Other quaternary ammonium compounds arelisted in the CTFA Cosmetic Ingredient Handbook, First Edition, on pages41-42, incorporated herein by reference.

A preferred fatty quaternary amine is Incroquat® Behenyl 18-MEA, whichis a mixture of behentrimonium methosulfate, C₁₀₋₄₀isoalkylamidopropylethyldimonium ethosulfate (Quaternium-33) and cetylalcohol, commercially available from Croda, Inc.

The amount of the at least one fatty quaternary amine in the compositionaccording to the sixth special embodiment is preferably in a range from0.001% to 2% by weight, more preferably from 0.01% to 1.0% by weight, inparticular from 0.1% to 0.5% by weight, based on the total weight of thecomposition.

Preferably, the composition according to the sixth special embodimentfurther comprises at least one surfactant. With regard to suitable andpreferred surfactants, reference is made to the surfactants mentionedbefore as component D). Preferably at least one nonionic surfactant isemployed. The amount of surfactant in the composition according to thesixth special embodiment is preferably in a range from 0.5% to 20% byweight, more preferably from 1.0% to 5.0% by weight, based on the totalweight of the composition.

Preferably, the composition according to the sixth special embodimentfurther comprises at least one ceramide. Ceramides may be used in thecomposition for moisturizing the fiber and maintaining cuticleintegrity. Ceramides are available by extraction from natural sources,or as synthetic ceramides and pseudoceramides. Preferred ceramides aree.g. 2-oleamido-1,3-octanediol and Ceramide II from Quest. Mixtures ofceramides are suitable, such as Ceramides LS from LaboratoriesSerobiologiques. The amount of ceramide in the composition according tothe sixth special embodiment is preferably in a range from 0.001% to0.5% by weight, more preferably from 0.01% to 0.5% by weight, inparticular from 0.01% to 0.1% by weight, based on the total weight ofthe composition.

Preferably, the composition according to the sixth special embodiment issubstantially anhydrous. The term “substantially anhydrous” means thatthe composition is either completely free of water or contains noappreciable amount of water, preferably no more than 5% by weight, andmore preferably no more than 1% by weight, based on the weight of thecomposition.

Suitable formulations are disclosed in US 2008/0131391 which isincorporated herein by reference. It was surprisingly found thatadvantageous properties are obtained, if the quaternary ammoniumpolymers a) used in the compositions according to this document arereplaced completely or partly by at least one imidazolium compound(=component a) according to the invention.

A seventh special embodiment is a cosmetic composition for treating akeratinous substrate, comprising in a cosmetically acceptable medium

-   -   at least one imidazolium compound (=component A), as defined        above and in the following, and    -   at least one alkoxysilanes with solubilizing functional groups.

With regard to suitable and preferred embodiments of component A),reference is made to the aforementioned general definition of theimidazolium compounds employed according to the invention. Suitablealkoxysilanes and formulations are disclosed in FR 2910276 A1 which isincorporated herein by reference.

Home Care Composition

A further aspect of the invention is a home care composition comprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one active ingredient and/or auxiliary.

The home care composition according to the invention can be acomposition that is effective against various microorganisms. Accordingto this variant, the imidazolium compound itself may act as activeingredient. Accordingly, in such a composition the use of a furtheractive ingredients and/or auxiliaries C) is only optional.

The home care composition according to the invention can also be acomposition that contains at least one imidazolium compound (componentA) as preservative. Accordingly, in such a composition the use of afurther component B) and/or C) is usually mandatory.

A typical home care composition according to the invention contains atleast one imidazolium compound A), optionally at least one furthermicrobicidal compound B), and at least one further component C),selected from non-ionic surfactants, anionic surfactants, amphotericsurfactants, water, alcohols and a combination thereof. The home carecompositions can include additional components C), such as enzymes,bleaches, whiteners, color care agents, fabric softeners, sudssuppressors, dispersants, dye transfer inhibitors, chelating agents,aerosol propellants, gelling agents, thickening agents and a combinationthereof.

The home care composition according to the invention can be formulatedin a variety of ways and may include a hydrophilic phase, a hydrophobicphase and optionally at least one emulsifying agent. The home carecomposition may be in the form of a liquids, semi-solid, paste, gel,bar, tablet, spray, foam, powder or granules.

For the purpose of the invention the term “home care composition” meansa composition for use in the general environment of human beings and isfurther described in the following. Home care compositions are generallynontoxic when applied in the vicinity of human beings, for example tofabrics and other items used by humans, when applied to surfaces usedby, or in the vicinity of, humans, or when applied to spaces occupied byhumans.

A further aspect of the invention is a method of using a home carecomposition, as defined above and in the following, by applying thecomposition to an article, surface or space. Exemplary articles,surfaces and spaces include clothes, furniture fabrics, rugs andcarpets, draperies, dishes and cooking utensils, grills, ovens, andother items used by humans. The term “surface” includes hard surfaces inthe human environment, such as floors, glass surfaces (such as glasswindows, doors and countertops), other counter surfaces, bath, toiletbowl, sink and other bathroom surfaces. The term “space” includes theinterior portion of buildings occupied by humans, including the aircontained therein.

Advantageously, a home care composition comprising at least oneimidazolium compound A) possesses effective antimicrobial preservativeproperties. Further, a home care composition comprising at least oneimidazolium compound A) also confers an antimicrobial effect onarticles, surfaces or spaces to which it is applied. Home carecompositions according to the invention include:

-   -   surface cleaning compositions (for example, glass, floor,        counter, bath, toilet bowl, sink, appliance and furniture        cleaning compositions);    -   deodorants (for example, solid, liquid and spray deodorants air        and/or surface deodorants);    -   disinfectants (for example, spray and solid air disinfectants        (including gel); and spray, solid, liquid and paste surface        disinfectants);    -   waxes and other surface protecting and/or polishing        compositions;    -   laundry compositions (for example detergents, fabric softeners        and whiteners); and    -   rug shampoos.

Preferably, the home care composition comprises the components A) and,if present, B) in a fraction of from about 0.001 to 50% by weight,particularly preferably 0.01 to 30% by weight, in particular 0.1 to 20%by weight, based on the total weight of the composition.

Pharmaceutical Composition

A further aspect of the invention is a pharmaceutical compositioncomprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one pharmaceutically acceptable active    ingredient, and-   D) optionally at least one pharmaceutically acceptable excipient.

The pharmaceutical composition according to the invention can be acomposition that is effective against various microorganisms. Accordingto this variant, the imidazolium compound itself may act aspharmaceutically active ingredient. Accordingly, in such a compositionthe use of a further pharmaceutically acceptable active ingredient C) isonly optional.

The pharmaceutical composition according to the invention can also be acomposition that contains at least one imidazolium compound (componentA) as preservative. Accordingly, in such a composition the use of afurther pharmaceutically acceptable active ingredient C) is usuallymandatory.

Preferably, the pharmaceutical composition comprises the components A)and, if present, B) in a fraction of from about 0.001 to 50% by weight,particularly preferably 0.01 to 30% by weight, in particular 0.1 to 20%by weight, based on the total weight of the composition.

The pharmaceutical composition of the invention is suitable foradministering in principle any type of active pharmaceutical ingredientC). These include benzodiazepines, antihypertensives, vitamins,cytostatics, in particular taxol, anesthetics, neuroleptics,antidepressants, antibiotics, antimycotics, fungicides,chemotherapeutics, urologics, thrombocyte aggregation inhibitors,sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroidtherapeutic agents, psychopharmacological agents, antiparkinsonians andother antihyperkinetic agents, ophthalmics, neuropathy preparations,calcium metabolism regulators, muscle relaxants, narcotics,antilipemics, hepatic therapeutic agents, coronary agents, cardiacs,immunotherapeutics, regulatory peptides and their inhibitors, hypnotics,sedatives, gynecological agents, antigouts, fibrinolytic agents, enzymepreparations and transport proteins, enzyme inhibitors, emetics,circulation-promoting agents, diuretics, diagnostics, corticoids,cholinergics, bile duct therapeutics, antiasthmatics, broncholytics,beta-receptor blockers, calcium antagonists, ACE inhibitors,antiarteriosclerotics, antiinflammatories, anticoagulants,antihypotensives, antihypoglycemics, antihypertonics, antifibrinolytics,antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics,antianemics, antiallergics, anthelmintics, analgesics, analeptics,aldosterone antagonists and slimming agents

Examples of suitable active ingredients C) are: acarbose, non-steroidalantirheumatics, cardiac glycosides, acetylsalicylic acid, virustatics,aclarubicin, acyclovir, cisplatin, actinomycin, alpha- andbeta-sympathomimetics, allopurinol, alosetron, alprostadil,prostaglandins, amantadine, ambroxol, amlodipine, methotrexate,5-aminosalicylic acid, amitriptyline, amlodipine, amoxicillin,anastrozole, atenolol, atorvastatin, azathioprine, balsalazide,beclomethasone, betahistine, bezafibrate, bicalutamide, diazepam anddiazepam derivatives, budesonide, bufexamac, buprenorphine, methadone,calcium salts, potassium salts, magnesium salts, candesartan,carbamazepine, captopril, cefalosporins, celetoxib, cetirizine,chenodeoxycholic acid, ursodeoxycholic acid, theophylline andtheophylline derivatives, trypsins, cimetidine, clarithromycin,clavulanic acid, clindamycin, clobutinol, clonidine, cotrimoxazole,codeine, caffeine, vitamin D and derivatives of vitamin D,colestyramine, cromoglicic acid, coumarin and coumarin derivatives,cysteine, cytarabine, cyclophosphamide, ciclosporin, cyproterone,cytarabine, dapiprazole, desogestrel, desonide, dihydralazine,diltiazem, ergot alkaloids, dimenhydrinate, dimethyl sulfoxide,dimethicone, dipyridamole, domperidone and domperidone derivatives,donepzil, dopamine, doxazosin, doxorubicin, doxylamine, dapiprazole,benzodiazepines, diclofenac, glycoside antibiotics, desipramine,econazole, ACE inhibitors, enalapril, ephedrine, epinephrine, epoetinand epoetin derivatives, morphinans, calcium antagonists, irinotecan,modafinil, orlistat, peptide antibiotics, phenytoin, riluzoles,risedronate, sildenafil, topiramate, macrolide antibiotics,esomeprazole, estrogen and estrogen derivatives, progestogen andprogestogen derivatives, testosterone and testosterone derivatives,androgen and androgen derivatives, ethenzamide, etofenamate, etofibrate,fenofibrate, etofylline, etoposide, famciclovir, famotidine, felodipine,fenofibrate, fentanyl, fenticonazole, gyrase inhibitor, fluconazole,fludarabine, flunarizine, fluorouracil, fluoxetine, flurbiprofen,ibuprofen, flutamide, fluvastatin, follitropin, formoterol, fosfomicin,furosemide, fusidic acid, galantamine, gallopamil, ganciclovir,gemfibrozil, gentamicin, ginkgo, St John's wort, glibenclamide, ureaderivatives as oral antidiabetics, glucagon, glucosamine and glucosaminederivatives, glutathione, glycerol and glycerol derivatives,hypothalamus hormones, goserelin, guanethidine, halofantrine,haloperidol, heparin and heparin derivatives, hyaluronic acid,hydralazine, hydrochlorothiazide and hydrochlorothiazide derivatives,salicylates, hydroxyzine, idarubicin, ifosfamide, imipramine,indometacin, indoramine, insulin, interferons, iodine and iodinederivatives, isoconazole, isoprenaline, glucitol and glucitolderivatives, itraconazole, ketoconazole, ketoprofen, ketotifen,lacidipine, lansoprazole, levodopa, levomethadone, thyroid hormones,lipoic acid and lipoic acid derivatives, lisinopril, lisuride,lofepramine, lomustine, loperamide, loratadine, maprotiline,mebendazole, mebeverine, meclozine, mefenamic acid, mefloquine,meloxicam, mepindolol, meprobamate, meropenem, mesalazine, mesuximide,metamizole, metformin, methotrexate, methylphenidate,methylprednisolone, metixen, metoclopramide, metoprolol, metronidazole,mianserin, miconazole, minocycline, minoxidil, misoprostol, mitomycin,mizolastine, moexipril, morphine and morphine derivatives, eveningprimrose, nalbuphine, naloxone, tilidine, naproxen, narcotine,natamycin, neostigmine, nicergoline, nicethamide, nifedipine, niflumicacid, nimodipine, nimorazole, nimustine, nisoldipine, adrenaline, andadrenaline derivatives, norfloxacin, novaminsulfone, noscapine,nystatin, ofloxacin, olanzapine, olsalazine, omeprazole, omoconazole,ondansetron, orlistat, oseltamivir, oxaceprol, oxacillin, oxiconazole,oxymetazoline, pantoprazole, paracetamol, paroxetine, penciclovir, oralpenicillins, pentazocine, pentifylline, pentoxifylline, perphenazine,pethidine, plant extracts, phenazone, pheniramine, barbituric acidderivatives, phenylbutazone, phenytoin, pimozide, pindolol, piperazine,piracetam, pirenzepine, piribedil, piroxicam, pramipexol, pravastatin,prazosin, procaine, promazine, propiverine, propranolol, propyphenazone,prostaglandins, protionamide, proxyphylline, quetiapine, quinapril,quinaprilate, ramipril, ranitidine, reproterol, reserpine, ribavirin,rifampicin, risperidone, ritonavir, ropinirol, rosiglitazone,roxatidine, roxithromycin, ruscogenin, rutoside and rutosidederivatives, sabadilla, salbutamol, salmeterol, scopolamine, selegiline,sertaconazole, sertindole, sertraline, silicates, simvastatin,sitosterol, sotalol, spaglumic acid, sparfloxacin, spectinomycin,spiramycin, spirapril, spironolactone, stavudine, streptomycin,sucralfate, sufentanil, sulbactam, sulfonamides, sulfasalazine,sulpiride, sultamicillin, sultiam, sumatriptan, suxamethonium chloride,tacrine, tacrolimus, taliolol, tamoxifen, taurolidine, tazarotene,tegaserod, temazepam, teniposide, tenoxicam, terazosin, terbinafine,terbutaline, terfenadine, terlipressin, tertatolol, tetracyclines,tetryzoline, theobromine, theophylline, butizine, thiamazole,phenothiazines, thiotepa, tiagabine, tiapride, propionic acidderivatives, ticlopidine, timolol, tinidazole, tioconazole, tioguanine,tioxolone, tiropramide, tizanidine, tolazoline, tolbutamide, tolcapone,tolnaftate, tolperisone, topotecan, torasemide, antiestrogens, tramadol,tramazoline, trandolapril, tranylcypromine, trapidil, trazodone,triamcinolone and triamcinolone derivatives, triamterene, trifluperidol,trifluridine, trimethoprim, trimipramine, tripelennamine, triprolidine,trifosfamide, tromantadine, trometamol, tropalpin, troxerutin,tulobuterol, tyramine, tyrothricin, urapidil, ursodeoxycholic acid,chenodeoxycholic acid, valaciclovir, valdecoxib, valproic acid,vancomycin, vecuronium chloride, venlafaxine, verapamil, vidarabine,vigabatrine, viloxazine, vinblastine, vincamine, vincristine, vindesine,vinorelbine, vinpocetine, viquidil, warfarin, xantinol nicotinate,xipamide, zafirlukast, zalcitabine, zanamivir, zidovudine, zolmitriptan,zolpidem, zopiclone, zotepine and the like.

The active ingredients can, if desired, also be used in the form oftheir pharmaceutically acceptable salts or derivatives, and in the caseof chiral active ingredients it is possible to employ both opticallyactive isomers and racemates or mixtures of diastereoisomers. Thecompositions of the invention can, if desired, also comprise two or moreactive pharmaceutical ingredients.

The formulation base of pharmaceutical compositions of the inventionpreferably comprises pharmaceutically acceptable excipients D).Pharmaceutically acceptable excipients are those known to be usable inthe area of pharmacy, food technology and adjacent sectors, inparticular the excipients listed in relevant pharmacopeias (e.g. DAB,Ph. Eur., BP, USP, JP) and others, whose properties do not stand in theway of physiological use.

Suitable excipients D) may be: lubricants, wetting agents, emulsifyingand suspending agents, antioxidants, anti-irritants, chelating agents,emulsion stabilizers, film formers, gel formers, odor-masking agents,resins, hydrocolloids, solvents, solubilizers, neutralizers, permeationpromoters, pigments, colorants, stabilizers, disintegrants, dessicants,opacifiers, thickeners, waxes, plasticizers, flavors, sweeteners,excipients to reduce permeation etc. An arrangement concerning this isbased on specialist knowledge as described for example in Fiedler, H. P.Lexikon der Hilfsstoffe für Pharmazie, Kosmetik and angrenzende Gebiete,4th edition, Aulendorf: ECV-Editio-Cantor-Verlag, 1996.

Plant Protection Composition

A further aspect of the invention is a plant protection compositioncomprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one active substance for plant protection,    and-   D) optionally at least one auxiliary.

The plant protection composition according to the invention can be acomposition that is effective against various microorganisms. Accordingto this variant, the imidazolium compound itself may act as activeingredient. Accordingly, in such a composition the use of a furtheractive substance for plant protection C) is only optional. Preferably,the plant protection composition in which the imidazolium compounditself acts as active ingredient is a fungicidal composition. Suchcompositions have been described in detail above.

The plant protection composition according to the invention can howeveralso be a composition that contains at least one imidazolium compound(component A) as preservative. Accordingly, in such a composition theuse of at least one further active substance for plant protection C) isusually mandatory.

The pharmaceutical composition of the invention is suitable in principleany type of active substance for plant protection C). Examples of atleast one active substance for plant protection are described in thefollowing.

Examples of fungicidal active substances C) comprise:

-   -   acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl;    -   amine derivatives, such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine        or tridemorph;    -   anilinopyrimidines, such as pyrimethanil, mepanipyrim or        cyprodinil;    -   antibiotics, such as cycloheximide, griseofulvin, kasugamycin,        natamycin, polyoxin and streptomycin;    -   azoles, such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, diniconazole, epoxiconazole, fenbuconazole,        fluquinconazole, flusilazole, flutriafol, hexaconazole,        imazalil, ipconazole, metconazole, myclobutanil, penconazole,        propiconazole, prochloraz, prothioconazole, tebuconazole,        tetraconazole, triadimefon, triadimenol, triflumizole or        triticonazole;    -   2-methoxybenzophenones, such as those disclosed in EP-A 897 904        by the general formula (I), e.g. metrafenone;    -   dicarboximides, such as iprodione, myclozolin, procymidone or        vinclozolin;    -   dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram or zineb;    -   heterocyclic compounds, such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadone, fenamidone, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        picobenzamid, probenazole, proquinazid, pyrifenox, pyroquilon,        quinoxyfen, silthiofam, thiabendazole, thifluzamide,        thiophanate-methyl, tiadinil, tricyclazole or triforine;    -   nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton        or nitrothal-isopropyl;    -   phenylpyrroles, such as fenpiclonil or fludioxonil;    -   unclassified fungicides, such as acibenzolar-S-methyl,        benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid,        cymoxanil, diclomezine, diclocymet, diethofencarb, edifenphos,        ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone,        fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb,        hexachlorobenzene, metrafenone, pencycuron, propamocarb,        phthalide, tolclofos-methyl, quintozene or zoxamide;    -   strobilurins, such as those disclosed in WO 03/075663 by the        general formula (I), for example azoxystrobin, dimoxystrobin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin and trifloxystrobin;    -   sulfenic acid derivatives, such as captafol, captan,        dichlofluanid, folpet or tolylfluanid;    -   cinnamamides and analogous compounds, such as dimethomorph,        flumetover or flumorph;    -   6-aryl-[1,2,4]triazolo[1,5-a]pyrimidines, such as those        disclosed, e.g., in WO 98/46608, WO 99/41255 or WO 03/004465, in        each case by the general formula (I);    -   amide fungicides, such as cyflufenamid and        (Z)—N-[α-(cyclopropylmethoxyimino)-2,3-difluoro-6-(difluoromethoxy)benzyl]-2-phenylacetamide.

Examples of herbicides C) comprise:

-   -   1,3,4-thiadiazoles, such as buthidazole and cyprazole;    -   amides, such as allidochlor, benzoylprop-ethyl, bromobutide,        chlorthiamid, dimepiperate, dimethenamid, diphenamid,        etobenzanid, flamprop-methyl, fosamine, isoxaben, metazachlor,        monalide, naptalam, pronamide or propanil;    -   aminophosphoric acids, such as bilanafos, buminafos,        glufosinate-ammonium, glyphosate or sulfosate;    -   aminotriazoles, such as amitrole, or anilides, such as anilofos        or mefenacet;    -   aryloxyalkanoic acid, such as 2,4-D, 2,4-DB, clomeprop,        dichlorprop, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB,        mecoprop, mecoprop-P, napropamide, naproanilide or triclopyr;    -   benzoic acids, such as chloramben or dicamba;    -   benzothiadiazinones, such as bentazon;    -   bleachers, such as clomazone, diflufenican, fluorochloridone,        flupoxam, fluridone, pyrazolate or sulcotrione;    -   carbamates, such as carbetamide, clorbufam, chlorpropham,        desmedipham, phenmedipham or vernolate;    -   quinolinecarboxylic acids, such as quinclorac or quinmerac;    -   dichloropropionic acids, such as dalapon;    -   dihydrobenzofurans, such as ethofumesate;    -   dhydrofuran-3-ones, such as flurtamone;    -   dinitroanilines, such as benefin, butralin, dinitramine,        ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin,        pendimethalin, prodiamine, profluralin, trifluralin;    -   dinitrophenols, such as bromofenoxim, dinoseb, dinoseb acetate,        dinoterb, DNOC or minoterb acetate;    -   diphenyl ethers, such as acifluorfen-sodium, aclonifen, bifenox,        chlornitrofen, difenoxuron, ethoxyfen, fluorodifen,        fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen,        nitrofen, nitrofluorfen or oxyfluorfen;    -   dipyridyls, such as cyperquat, difenzoquat metilsulfate, diquat        or paraquat dichloride;    -   imidazoles, such as isocarbamid;    -   imidazolinones, such as imazamethapyr, imazapyr, imazaquin,        imazethabenzmethyl, imazethapyr, imazapic or imazamox;    -   oxadiazoles, such as methazole, oxadiargyl or oxadiazone;    -   oxiranes, such as tridiphane;    -   phenols, such as bromoxynil or ioxynil;    -   phenoxyphenoxypropionic acid esters, such as clodinafop,        cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl,        fenoxaprop-P-ethyl, fenthiaprop-ethyl, fluazifop-butyl,        fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl,        haloxyfop-P-methyl, isoxapyrifop, propaquizafop,        quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-P-tefuryl;    -   phenylacetic acids, such as chlorfenac;    -   phenylpropionic acids, such as chlorphenprop-methyl;    -   ppi-active substances (ppi=preplant incorporated), such as        benzofenap, flumiclorac-pentyl, flumioxazin, flumipropyn,        flupropacil, pyrazoxyfen, sulfentrazone or thidiazimin;    -   pyrazoles, such as nipyraclofen;    -   pyridazines, such as chloridazon, maleic hydrazide, norflurazon        or pyridate;    -   pyridinecarboxylic acids, such as clopyralid, dithiopyr,        picloram or thiazopyr;    -   pyrimidyl ethers, such as pyrithiobac acid, pyrithiobac-sodium,        KIH-2023 or KIH-6127;    -   sulfonamides, such as flumetsulam or metosulam;    -   triazolecarboxamides, such as triazofenamide;    -   uracils, such as bromacil, lenacil or terbacil;    -   furthermore benazolin, benfuresate, bensulide, benzofluor,        bentazon, butamifos, cafenstrole, chlorthal-dimethyl,        cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide,        perfluidone, piperophos, topramezone and prohexadione-calcium;    -   sulfonylureas, such as amidosulfuron, azimsulfuron,        bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,        cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl,        flazasulfuron, halosulfuron-methyl, imazosulfuron,        metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron,        pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl,        thifensulfuron-methyl, triasulfuron, tribenuron-methyl,        triflusulfuron-methyl or tritosulfuron;    -   plant protection active substances of the cyclohexenone type,        such as alloxydim, clethodim, cloproxydim, cycloxydim,        sethoxydim and tralkoxydim. Very particularly preferred        herbicidal active substances of the cyclohexenone type are:        tepraloxydim (cf. AGROW, No. 243, 11.3.95, page 21, caloxydim)        and        2-(1-[2-{4-chlorphenoxy}propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothio-pyran-3-yl)-2-cyclohexen-1-one,        and of the sulfonylurea type is:        N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-triazin-2-yl)amino)carbonyl)-2-(trifluoromethyl)benzenesulfonamide.

Examples of insecticides C) comprise:

-   -   organophosphates, such as acephate, azinphos-methyl,        chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos,        dimethylvinphos, dioxabenzofos, dicrotophos, dimethoate,        disulfoton, ethion, EPN, fenitrothion, fenthion, isoxathion,        malathion, methamidophos, methidathion, methyl parathion,        mevinphos, monocrotophos, oxydemeton-methyl, paraoxon,        parathion, phenthoate, phosalone, phosmet, phosphamidon,        phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos,        pirimiphos-ethyl, pyraclofos, pyridaphenthion, sulprophos,        triazophos, trichlorfon, tetrachlorvinphos or vamidothion;    -   carbamates, such as alanycarb, benfuracarb, bendiocarb,        carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,        indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur,        thiodicarb or triazamate;    -   pyrethroids, such as bifenthrin, cyfluthrin, cycloprothrin,        cypermethrin, deltamethrin, esfenvalerate, etofenprox,        fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin,        permethrin, silafluofen, tau-fluvalinate, tefluthrin,        tralomethrin, alpha-cypermethrin or zeta-cypermethrin;    -   arthropodal growth regulators: a) chitin synthesis inhibitors,        e.g. benzoylureas, such as chlorfluazuron, diflubenzuron,        flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,        teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox,        etoxazole or clofentezine; b) ecdysone antagonists, such as        halofenozide, methoxyfenozide or tebufenozide; c) juvenile        hormone mimics, such as pyriproxyfen, methoprene or        fenoxycarb; d) lipid biosynthesis inhibitors such as        spirodiclofen;    -   neonicotinoids, such as flonicamid, clothianidin, dinotefuran,        imidacloprid, thiamethoxam, nitenpyram, nithiazine, acetamiprid        or thiacloprid;    -   additional unclassified insecticides, such as abamectin,        acequinocyl, acetamiprid, amitraz, azadirachtin, bensultap,        bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazine,        diafenthiuron, dinotefuran, diofenolan, emamectin, endosulfan,        ethiprole, fenazaquin, fipronil, formetanate, formetanate        hydrochloride, gamma-HCH, hydramethylnon, imidacloprid,        indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine,        spinosad, tebufenpyrad, thiamethoxam, thiocyclam, XMC and        xylylcarb;    -   N-phenylsemicarbazones, such as those disclosed in EP-A 462 456        by the general formula (I), especially compounds of the general        formula (A)

in which R² and R³ represent, independently of one another, hydrogen,halogen, CN, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl or C₁-C₄haloalkoxy and R⁴ represents C₁-C₄ alkoxy, C₁-C₄ haloalkyl or C₁-C₄haloalkoxy, e.g. compound IV, in which R² represents 3-CF₃, R³represents 4-CN and R⁴ represents 4-OCF₃.

Useable growth regulators C) are, e.g., chlormequat chloride, mepiquatchloride, prohexadione-calcium or the group of the gibberellins. Theseinclude, e.g. the gibberellin GA₁, GA₃, GA₄, GA₅ and GA₇, and the like,and the corresponding exo-16,17-dihydrogibberellins, and also thederivatives thereof, e.g. the esters with C₁-C₄ carboxylic acids, Theexo-16,17-dihydro-GA₅ 13-acetate is preferred according to theinvention.

Antimicrobial Polymer Composition or Coating Composition

The imidazolium compounds employed according to the invention are inparticular suitable to provide antimicrobial polymers and coatingcompositions, for example compositions for medical applications. Thepolymer compositions and coating compositions show an outstandingantimicrobial activity. Thus, in a further aspect, the inventionprovides an antimicrobial polymer composition or coating composition,wherein the polymer composition or the coating comprises an effectiveantimicrobial amount of at least one polymeric, ionic compoundcomprising imidazolium groups (component A), as defined above.

Preferably, the polymer composition or coating composition comprises atleast one imidazolium compound in an amount of from about 0.001 to about15.0 weight percent, more preferably 0.01 to 10.0 weight percent, basedon the total weight of the polymer composition or the coatingcomposition.

A further aspect of the invention is a polymer composition or coatingcomposition, comprising

-   A) at least one imidazolium compound as defined above,-   B) optionally at least one further microbicidal compound different    from the compounds of component (A),-   C) optionally at least one polymer and/or at least one polymerizable    compound, and-   D) optionally at least one additive.

With regard to suitable and preferred compounds of the components A) andB), reference is made to the aforementioned description of suitable andpreferred embodiments of those components.

The employed polymers may be in any form, for example fibers, films ormolded parts. They may be for example woven or nonwoven polymer fabrics.

Suitable polymers C) may be selected from:

-   -   1. Polymers of monoolefins and diolefins, for example        polypropylene, polyisobutylene, polybut-1-ene,        poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well        as polymers of cycloolefins, for instance of cyclopentene or        norbornene, polyethylene (which optionally can be crosslinked),        for example high density polyethylene (HDPE), low density        polyethylene (LDPE), linear low density polyethylene (LLDPE),        branched low density polyethylene (BLDPE) and medium density        polyethylene (MDPE).        -   Polyolefins, i.e. the polymers of monoolefins exemplified in            the preceding paragraph, preferably polyethylene and            polypropylene, can be prepared by different, and especially            by the following, methods:        -   a) radical polymerization (normally under high pressure and            at elevated temperature).        -   b) catalytic polymerization using a catalyst that normally            contains one or more than one metal of groups IVb, Vb, VIb            or VIII of the Periodic Table. These metals usually have one            or more than one ligand, typically oxides, halides,            alcoholates, esters, ethers, amines, alkyls, alkenyls and/or            aryls that may be either p- or s-coordinated. These metal            complexes may be in the free form or fixed on substrates,            typically on activated magnesium chloride, titanium(III)            chloride, alumina or silicon oxide. These catalysts may be            soluble or insoluble in the polymerization medium. The            catalysts can be used by themselves in the polymerization or            further activators may be used, typically metal alkyls,            metal hydrides, metal alkyl halides, metal alkyl oxides or            metal alkyloxanes, said metals being elements of groups Ia,            IIa and/or IIIa of the Periodic Table. The activators may be            modified conveniently with further ester, ether, amine or            silyl ether groups. These catalyst systems are usually            termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ            (DuPont), metallocene or single site catalysts (SSC).    -   2. Mixtures of the polymers mentioned under 1), for example        mixtures of polypropylene with polyisobutylene, polypropylene        with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of        different types of polyethylene (for example LDPE/HDPE).    -   3. Copolymers of monoolefins and diolefins with each other or        with other vinyl monomers, for example ethylene/propylene        copolymers, linear low density polyethylene (LLDPE) and mixtures        thereof with low density polyethylene (LDPE),        propylene/but-1-ene copolymers, propylene/isobutylene        copolymers, ethylene/but-1-ene copolymers, ethylene/hexene        copolymers, ethylene/methylpentene copolymers, ethylene/heptene        copolymers, ethylene/octene copolymers, propylene/butadiene        copolymers, isobutylene/isoprene copolymers, ethylene/alkyl        acrylate copolymers, ethylene/alkyl methacrylate copolymers,        ethylene/vinyl acetate copolymers and their copolymers with        carbon monoxide or ethylene/acrylic acid copolymers and their        salts (ionomers) as well as terpolymers of ethylene with        propylene and a diene such as hexadiene, dicyclopentadiene or        ethylidenenorbornene; and mixtures of such copolymers with one        another and with polymers mentionedin 1) above, for example        polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl        acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers        (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random        polyalkylene/carbon monoxide copolymers and mixtures thereof        with other polymers, for example polyamides.    -   4. Hydrocarbon resins (for example C5-C9) including hydrogenated        modifications thereof (e.g. tackifiers) and mixtures of        polyalkylenes and starch.    -   5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).    -   6. Copolymers of styrene or [alpha-methylstyrene with dienes or        acrylic derivatives, for example styrene/butadiene,        styrene/unsaturated ester, styrene/acrylonitrile, styrene/alkyl        methacrylate, styrene/butadiene/alkyl acrylate,        styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,        styrene/acrylonitrile/methyl acrylate; mixtures of high impact        strength of styrene copolymers and another polymer, for example        a polyacrylate, a diene polymer or an ethylene/propylene/diene        terpolymer; and block copolymers of styrene such as        styrene/butadiene/styrene, styrene/isoprene/styrene,        styrene/ethylene/butylene/styrene or        styrene/ethylene/propylene/styrene.    -   7. Graft copolymers of styrene or [alpha-methylstyrene, for        example styrene on polybutadiene, styrene on        polybutadiene-styrene or polybutadiene-acrylonitrile copolymers;        styrene and acrylonitrile (or methacrylonitrile) on        polybutadiene; styrene, acrylonitrile and methyl methacrylate on        polybutadiene; styrene and maleic anhydride on polybutadiene;        styrene, acrylonitrile and maleic anhydride or maleimide on        polybutadiene; styrene and maleimide on polybutadiene; styrene        and alkyl acrylates or methacrylates on polybutadiene; styrene        and acrylonitrile on ethylene/propylene/diene terpolymers;        styrene and acrylonitrile on polyalkyl acrylates or polyalkyl        methacrylates, styrene and acrylonitrile on acrylate/butadiene        copolymers, as well as mixtures thereof with the copolymers        listed under 6), for example the copolymer mixtures known as        ABS, SAN, MBS, ASA or AES polymers.    -   8. Halogen-containing polymers such as polychloroprene,        chlorinated rubbers, chlorinated or sulfochlorinated        polyethylene, copolymers of ethylene and chlorinated ethylene,        epichlorohydrin homo- and copolymers, especially polymers of        halogen-containing vinyl compounds, for example polyvinyl        chloride, polyvinylidene chloride, polyvinyl fluoride,        polyvinylidene fluoride, as well as copolymers thereof such as        vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate        or vinylidene chloride/vinyl acetate copolymers.    -   9. Polymers derived from α,β-unsaturated acids and derivatives        thereof such as polyacrylates and polymethacrylates; polymethyl        methacrylates, polyacrylamides and polyacrylonitriles,        impact-modified with butyl acrylate.    -   10. Copolymers of the monomers mentioned under 9) with each        other or with other unsaturated monomers, for example        acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate        copolymers, acrylonitrile/alkoxyalkyl acrylate or        acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl        methacrylate/butadiene terpolymers.    -   11. Polymers derived from unsaturated alcohols and amines or the        acyl derivatives or acetals thereof, for example polyvinyl        alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl        benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl        phthalate or polyallyl melamine; as well as their copolymers        with olefins mentionedin 1) above.    -   12. Homopolymers and copolymers of cyclic ethers such as        polyalkylene glycols, polyethylene oxide, polypropylene oxide or        copolymers thereof with bis-glycidyl ethers.    -   13. Polyacetals such as polyoxymethylene and those        polyoxymethylenes which contain ethylene oxide as a comonomer;        polyacetals modified with thermoplastic polyurethanes, acrylates        or MBS.    -   14. Polyphenylene oxides and sulfides, and mixtures of        polyphenylene oxides with styrene polymers or polyamides.    -   15. Polyurethanes derived from hydroxyl-terminated polyethers,        polyesters or polybutadienes on the one hand and aliphatic or        aromatic polyisocyanates on the other, as well as precursors        thereof.    -   16. Polyamides and copolyamides derived from diamines and        dicarboxylic acids and/or from aminocarboxylic acids or the        corresponding lactams, for example polyamide 4, polyamide 6,        polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11,        polyamide 12, aromatic polyamides starting from m-xylene diamine        and adipic acid; polyamides prepared from hexamethylenediamine        andisophthalic or/and terephthalic acid and with or without an        elastomer as modifier, for example        poly-2,4,4,-trimethylhexamethylene terephthalamide or        poly-m-phenylene isophthalamide; and also block copolymers of        the aforementioned polyamides with polyolefins, olefin        copolymers, ionomers or chemically bonded or grafted elastomers;        or with polyethers, e.g. with polyethylene glycol, polypropylene        glycol or polytetramethylene glycol; as well as polyamides or        copolyamides modified with EPDM or ABS; and polyamides condensed        during processing (RIM polyamide systems).    -   17. Polyureas, polyimides, polyamide-imides and        polybenzimidazoles.    -   18. Polyesters derived from dicarboxylic acids and diols and/or        from hydroxycarboxylic acids or the corresponding lactones, for        example polyethylene terephthalate, polytrimethylene        terephthalate, polybutylene terephthalate,        poly-1,4-dimethylolcyclohexane terephthalate and        polyhydroxybenzoates, as well as block copolyether esters        derived from hydroxyl-terminated polyethers; and also polyesters        modified with polycarbonates or MBS. Polyesters and polyester        copolymers as defined in U.S. Pat. No. 5,807,932 (column 2, line        53), incorporated herein by reference.    -   19. Polycarbonates and polyester carbonates.    -   20. Polysulfones, polyether sulfones and polyether ketones.    -   21. Crosslinked polymers derived from aldehydes on the one hand        and phenols, ureas and melamines on the other hand, such as        phenol/formaldehyde resins, urea/formaldehyde resins and        melamine/formaldehyde resins.    -   22. Drying and non-drying alkyd resins.    -   23. Unsaturated polyester resins derived from copolyesters of        saturated and unsaturated dicarboxylic acids with polyhydric        alcohols and vinyl compounds as crosslinking agents, and also        halogen-containing modifications thereof of low flammability.    -   24. Crosslinkable acrylic resins derived from substituted        acrylates, for example epoxy acrylates, urethane acrylates or        polyester acrylates.    -   25. Alkyd resins, polyester resins and acrylate resins        crosslinked with melamine resins, urea resins, polyisocyanates        or epoxy resins.    -   26. Crosslinked epoxy resins derived from polyepoxides, for        example from bis glycidyl ethers or from cycloaliphatic        diepoxides.    -   27. Natural polymers such as cellulose, rubber, gelatin and        chemically modified homologous derivatives thereof, for example        cellulose acetates, cellulose propionates and cellulose        butyrates, or the cellulose ethers, such as methyl cellulose; as        well as rosins and their derivatives.    -   28. Blends of the aforementioned polymers (polyblends), for        example PP/EPDM, Polyamide/-EPDM or ABS, PVC/EVA, PVC/ABS,        PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE,        PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,        POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,        PA/HDPE, PA/PP, PA/PPO.    -   29. Naturally occurring and synthetic organic materials which        are pure monomeric compounds or mixtures of such compounds, for        example mineral oils, animal and vegetable fats, oil and waxes,        or oils, fats and waxes based on synthetic esters (e.g.        phthalates, adipates, phosphates or trimellitates) and also        mixtures of synthetic esters with mineral oils in any weight        ratios, typically those used as spinning compositions, as well        as aqueous emulsions of such materials.    -   30. Aqueous emulsions of natural or synthetic rubber, e.g.        natural latex or latices of carboxylated styrene/butadiene        copolymers.    -   31. Polysiloxanes such as the soft, hydrophilic polysiloxanes        described, for example, in U.S. Pat. No. 4,259,467; and the hard        polyorganosiloxanes described, for example, in U.S. Pat. No.        4,355,147.    -   32. Silicone elastomers, for example liquid silicone rubbers        (LSR). Liquid Silicone Rubbers are available from Dow Chemical        and are described for example in U.S. Pat. Nos. 6,569,536;        6,420,038; 6,297,291; 6,218,466; 6,130,272; 5,994,461;        5,989,719; 5,973,030; 5,908,888; 5,880,199; 5,877,256;        5,859,094; 5,789,084 and 5,661,210. The disclosures of these        U.S. patents are incorporated by reference.    -   33. Polyketimines in combination with unsaturated acrylic        polyacetoacetate resins or with unsaturated acrylic resins. The        unsaturated acrylic resins include the urethane acrylates,        polyether acrylates, vinyl or acryl copolymers with pendant        unsaturated groups and the acrylated melamines. The        polyketimines are prepared from polyamines and ketones in the        presence of an acid catalyst.    -   34. Radiation curable compositions containing ethylenically        unsaturated monomers or oligomers and a polyunsaturated        aliphatic oligomer.    -   35. Epoxymelamine resins such as light-stable epoxy resins        crosslinked by an epoxy functional coetherified high solids        melamine resin such as LSE-4103 (Monsanto).

Included also are thermoplastic olefin (TPO), thermoplastic elastomers,polyetherimide, polymethylpentene, polyphenylene ether, polyphenylenesulfide, polysulfone or polytetrafluoroethylene (PTFE).

Some polymers of specific technical interest include:

Polysulfone (PSF) Polyethersulfone (PES) Polyphenylsulfone (PPS)Polyvinylidene Fluoride (PVDF) Polypropylene (PP) Polyethylene (PE)

Cellulose, Cellulose acetates (CA), Cellulose nitrate

Polyamide (PA) Polyacrylonitrile (PAN) Polytetrafluoroethylene (PTFE)Polycarbonate (PC) Polymethylmethacrylate (PMMA).

In particular, the present polymers are those that are typicallyemployed in medical applications, for example polyurethanes,polycarbonate, liquid silicone rubbers, polyethylene, polypropylene,polyethylene/polypropylene copolymers or polymer composites.

Polymer composites are for instance natural products composites, forexample a natural product mixed with a thermoplastic polymer such as apolyolefin. Such composites are disclosed in published U.S. app. No.20040235983, the disclosure of which is hereby incorporated byreference. Natural products are for instance wood flour, flax, hemp,jute, kenaf or rice husk. The thermoplastic polymer is for instancepolyethylene or polypropylene.

A preferred polymer composition or coating composition according to theinvention additionally contains, for example, one or more components D)selected from antioxidants, light stabilizers (such as UV absorbersand/or sterically hindered amines, phosphites, phosphonites), metaldeactivators, nucleating agents, fillers, plasticisers, pigments,flameproofing agents, antistatic agents, lubricants, emulsifiers,rheology additives, catalysts, flow-control agents, optical brighteners,blowing agents and combinations thereof.

The employed components D), in particular the antioxidants, lightstabilizers, and metal deactivators, preferably have a high migrationfastness and temperature resistance.

Suitable antioxidants D) are selected from the following classes:

-   1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,    2,6-di-tert-butyl-4-ethylphenol, etc;-   2. Alkylthiomethylphenols, for example    2,4-dioctylthiomethyl-6-tert-butylphenol,    2,4-dioctylthiomethyl-6-methylphenol,    2,4-dioctylthiomethyl-6-ethylphenol,    2,6-di-dodecylthiomethyl-4-nonylphenol, etc;-   3. Hydroquinones and alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,    2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,    2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyanisole,    3,5-di-tert-butyl-4-hydroxyphenyl stearate,    bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate, etc;-   4. Tocopherols;-   5. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methylphenol),    2,2′-thiobis(4-octylphenol),    4,4′-thiobis(6-tert-butyl-3-methylphenol),    4,4′-thiobis(6-tert-butyl-2-methylphenol),    4,4′-thiobis(3,6-di-sec-amylphenol),    4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide, etc;-   6. Alkylidenebisphenols, for example    2,2′-methylenebis(6-tert-butyl-4-methylphenol),    2,2′methylenebis(6-tert-butyl-4-ethylphenol),    2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol,    1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,    2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,    2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,    1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, etc;-   7. O-, N- and S-benzyl compounds, for example    3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,    octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,    tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,    tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,    bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalate,    bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,    isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, etc;-   8. Hydroxybenzylated malonates, for example    dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,    di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,    didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-malonate,    bis[4-(1,1,3,3-tetramethylbutyl)phenyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,    etc;-   9. Aromatic hydroxybenzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,    1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,    2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-phenol, etc;-   10. Triazine compounds, for example    2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,    2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,    2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,    1,3,5-tris(3,5-di-tert-butyl-4-hyphenylpropionyl)-hexahydro-1,3,5-triazine,    1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, etc.-   11. Benzylphosphonates, for example    dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,    diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,    dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the    calcium salt of the monoethyl ester of    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, etc;-   12. Acylaminophenols, for example 4-hydroxylauranilide,    4-hydroxystearanilide, octyl    N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, etc;-   13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols;-   14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols;-   15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols;-   16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with    mono- or polyhydric alcohols;-   Suitable mono- or polyhydric alcohols for compounds 13.) to 16.) are    methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,    1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,    thiodiethylene glycol, diethylene glycol, triethylene glycol,    pentaerythritol, tris(hydroxyethyl)isocyanurate,    N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,    trimethylhexanediol, trimethylolpropane,    4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2octane.-   17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    e.g.    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,    N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyphydrazide,    N,N′-bis[2-(3-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyloxy)ethyloxamide    (Naugard®XL-1, supplied by Uniroyal).-   18. Ascorbic Acid (Vitamin C)-   19. Aminic antioxidants, for example    N,N′-di-isopropyl-p-phenylenediamine,    N,N′-di-sec-butyl-p-phenylenediamine,    N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,    N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,    N,N′-bis(1-methylheptyl)-p-phenylenediamine,    N,N′-dicyclohexyl-p-phenylenediamine,    N,N′-diphenyl-p-phenylenediamine,    N,N′-bis(2-naphthyl)-p-phenylenediamine,    N-isopropyl-N′-phenyl-p-phenylenediamine,    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,    N-cyclohexyl-N′-phenyl-p-phenylenediamine,    4-(p-toluenesulfamoyl)diphenylamine,    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,    N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,    N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,    N-phenyl-2-naphthylamine, octylated diphenylamine, for example    p,p′-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol,    4-butyrylaminophenol, 4-nonanoylaminophenol,    4-dodecanoylaminophenol, 4-octadecanoylaminophenol,    bis(4-methoxy-phenyl)amine,    2,6-di-tert-butyl-4-dimethylaminomethylphenol,    2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,    N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,    1,2-bis[(2-methylphenyl)aminoethane, 1,2-bis(phenyl-amino)propane,    (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenylamine,    tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and    dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-    and dialkylated nonyldiphenylamines, a mixture of mono- and    dialkylated dodecyldiphenylamines, a mixture of mono- and    dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and    dialkylated tert-butyldiphenylamines,    2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a    mixture of mono- and dialkylated    tert-butyl/tert-octylphenothiazines, a mixture of mono- and    dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,    N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

Suitable light stabilizers (UV absorbers) and metal deactivators areselected, for example, from groups a) to s):

a) 4,4-diarylbutadienes,b) cinnamic esters,c) benzotriazoles,d) hydroxybenzophenones,e) diphenylcyanoacrylates,f) oxamides,g) 2-phenyl-1,3,5-triazines;h) antioxidants,i) nickel compounds,j) sterically hindered amines,k) metal deactivators,I) phosphites and phosphonites,m) hydroxylamines,n) nitrones,o) amine oxides,p) benzofuranones and indolinones,q) thiosynergists,r) peroxide scavengers, ands) basic costabilizers.

The antimicrobial compounds A), optional B) and optional additives D)may be added to at least one polymer and/or at least one polymerizablecompound C) individually or mixed with one another. If desired, theindividual components can be mixed with one another before incorporationinto the polymer or polymerizable composition for example by dryblending.

The incorporation of the biocides of the invention can be carried out byknown methods, such as dry blending in the form of a powder or wetmixing in the form of solutions, dispersions or suspensions for examplein an inert solvent, water or oil. The biocides of the invention may beincorporated, for example, before or after molding or also by applyingthe dissolved or dispersed biocide (or an additive mixture containingthe biocide) to the polymer material or the polymerisable composition,with or without subsequent evaporation of the solvent or thesuspension/dispersion agent. They may be added directly into theprocessing apparatus (e.g. extruders, internal mixers, etc), e.g. as adry mixture or powder or as solution or dispersion or suspension.

The incorporation can be carried out e.g. in any heatable containerequipped with a stirrer, e.g. in a closed apparatus such as a kneader,mixer or stirred vessel. The incorporation is preferably carried out inan extruder or in a kneader. The processing may take place in an inertatmosphere or in the presence of oxygen.

The addition of biocide (or an additive mixture containing the biocide)to the polymer substrate can be carried out in all customary mixingmachines in which the polymer is melted and mixed with the additives.Suitable machines are known to those skilledin the art. They arepredominantly mixers, kneaders and extruders.

Processing includes extrusion, co-kneading, pultrusion, compressionmolding, sheet extrusion, thermoforming, injection molding or rotationalmolding. The process is preferably carried out in an extruder byintroducing the additives during processing.

Particularly preferred processing machines are single-screw extruders,contrarotating and corotating twin-screw extruders, rotomolding devices,planetary-gear extruders, ring extruders or cokneaders. It is alsopossible to use processing machines provided with at least one gasremoval compartment to which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

The biocide (or an additive mixture containing the biocide) can also beadded to the polymer in the form of a masterbatch (“concentrate”) whichcontains the components in a concentration of, for example, about 1% toabout 40% and preferably about 2% to about 20% by weight incorporated ina polymer. The polymer must not necessarily be identical to the polymerwhere the additives are added finally. In such operations, the polymercan be used in the form of powder, granules, solutions, suspensions orin the form of latices. Incorporation can take place prior to or duringthe shaping operation, or by applying the dispersed compound to thepolymer, with or without subsequent evaporation of the solvent. Afurther possibility for incorporating the biocide of the invention (oran additive mixture containing the biocide) into polymer substrates isto add them before, during or directly after the polymerization of thecorresponding monomers or prior to crosslinking. In this context theadditives of the invention can be added as it is or else in encapsulatedform (for example in waxes, oils or polymers).

The polymers containing the biocide (or an additive mixture containingthe biocide) described herein can be used for the production ofmoldings, rotomolded articles, injection molded articles, blow moldedarticles, profiles, films, woven and nonwoven fabrics, and the like.

When the polymer composition or coating composition according to theinvention is used in the medical sector, it is for example a catheter,hose, tube, valve, articles for urology, bone cement, fabric,toothbrushes, silicone plastics, films, textiles, diapers and the like.

The coating composition according to the invention usually contains afilm forming binder.

The binder can in principle be any binder which is customary inindustry, for example those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim1991. In general, it is a film forming binder based on a thermoplasticor thermosetting resin, predominantly on a thermosetting resin. Examplesthereof are alkyd, acrylic, acrylic alkyd, polyester, phenolic,melamine, epoxy and polyurethane resins and mixtures thereof. The bindercan be a cold-curable or hot-curable binder; the addition of a curingcatalyst may be advantageous. Suitable catalysts which accelerate curingof the binder are described, for example, in Ullmann's Encyclopedia ofIndustrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft,Weinheim 1991.

The coating compositions according to the invention are for exampleemployed as a top coat for plastics or metal or as a wood coating.

Examples of coatings compositions containing specific binders are:

-   1. paints based on cold- or hot-crosslinkable alkyd, acrylate,    polyester, epoxy or melamine resins or mixtures of such resins, if    desired with addition of a curing catalyst;-   2. two-component polyurethane paints based on hydroxyl-containing    acrylate, polyester or polyether resins and aliphatic or aromatic    isocyanates, isocyanurates or polyisocyanates;-   3. one-component polyurethane paints based on blocked isocyanates,    isocyanurates or polyisocyanates which are deblocked during baking,    if desired with addition of a melamine resin;-   4. one-component polyurethane paints based on a    trisalkoxycarbonyltriazine crosslinker and a hydroxyl group    containing resin such as acrylate, polyester or polyether resins;-   5. one-component polyurethane paints based on aliphatic or aromatic    urethaneacrylates or polyurethaneacrylates having free amino groups    within the urethane structure and melamine resins or polyether    resins, if necessary with curing catalyst;-   6. two-component paints based on (poly)ketimines and aliphatic or    aromatic isocyanates, isocyanurates or polyisocyanates;-   7. two-component paints based on (poly)ketimines and an unsaturated    acrylate resin or a polyacetoacetate resin or a    methacrylamidoglycolate methyl ester;-   8. two-component paints based on carboxyl- or amino-containing    polyacrylates and polyepoxides;-   9. two-component paints based on acrylate resins containing    anhydride groups and on a polyhydroxy or polyamino component;-   10. two-component paints based on acrylate-containing anhydrides and    polyepoxides;-   11. two-component paints based on (poly)oxazolines and acrylate    resins containing anhydride groups, or unsaturated acrylate resins,    or aliphatic or aromatic isocyanates, isocyanurates or    polyisocyanates;-   12. two-component paints based on unsaturated polyacrylates and    polymalonates;-   13. thermoplastic polyacrylate paints based on thermoplastic    acrylate resins or externally crosslinking acrylate resins in    combination with etherified melamine resins;-   14. paint systems based on siloxane-modified or fluorine-modified    acrylate resins.

The coating compositions may also comprise further components, examplesbeing solvents, pigments, dyes, plasticizers, stabilizers, thixotropicagents, drying catalysts and/or levelling agents. Examples of possiblecomponents are those described in Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds, such as organotin compounds, for example.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconiumchelates of acetylacetone, ethyl acetylacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate,and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate.

Examples of amines are, in particular, tertiary amines, for exampletributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof. Furtherexamples are quaternary ammonium salts, for exampletrimethylbenzyl-ammonium chloride.

Amino-containing resins are simultaneously binder and curing catalyst.Examples thereof are amino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

The coating compositions can also be radiation-curable coatingcompositions. In this case, the binder essentially comprises monomericor oligomeric compounds containing ethylenically unsaturated bonds,which after application are cured by actinic radiation, i.e. convertedinto a crosslinked, high molecular weight form. Where the system isUV-curing, it generally contains a photoinitiator as well. Correspondingsystems are described in the above mentioned publication Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages451-453.

The coating compositions according to the invention can be applied toany desired substrates, for example to metal, wood, plastic, ceramicmaterials or plastic wood composites.

The coating compositions according to the invention are also suitablefor protecting a wood surface. In this case, the coating compositionscan be applied in form of a varnish, paint, etc or by impregnation. Afurther aspect of the invention is a method for providing antimicrobialactivity to a wood surface which method comprises applying a presentcoatings composition, especially a varnish, paint, stain or impregnationon wood. The coating composition may be applied by impregnation or asbase coat (primer) or top coat.

If the coating composition is employed for protecting a wood surface,preferably a solvent is used, selected e.g. from the group consisting ofaliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatichydrocarbons, alcohols, ethers, esters, ketones, glycols, glycol ethers,glycol esters, polyglycols or mixtures thereof. Preferably, in this casethe binder is selected from the group consisting of alkyd resins,modified alkyd resins, autocrosslinking or non-autocrosslinking acrylicresins, polyester resins, drying oils, phenolic resins, nitrocelluloseor mixtures thereof.

Other additives like fungicides or insecticides are possible. Suitablecomponents are known to the skilled artisan.

Any coating composition suitable for coating wood may be used as a topcoat. It will normally contain a binder, dissolved or dispersed in anorganic solvent or in water or a mixture of water and solvent. Thebinder may typically be a surface coating resin which dries in the airor hardens at room temperature. Exemplary of such binders arenitrocellulose, polyvinyl acetate, polyvinyl chloride, unsaturatedpolyester resins, polyacrylates, polyurethanes, epoxy resins, phenolicresins, and especially alkyd resins. The binder may also be a mixture ofdifferent surface coating resins. Provided the binders are curablebinders, they are normally used together with a hardener and/oraccelerator.

The top coat may also be a radiation-curable, solvent-free formulationof photopolymerizable compounds. Illustrative examples are mixtures ofacrylates or methacrylates, unsaturated polyester/styrene mixtures ormixtures of other ethylenically unsaturated monomers or oligomers.

The top coat may contain a soluble dye and/or a pigment and/or a filler.The pigment may be an organic, inorganic or metallic pigment. Thepigments may be opaque or transparent, such as for example transparentiron oxides. The filler may be typically kaolin, calcium carbonate oraluminium silicate. Preferably, the top coat is a clear varnish, i.e. itcontains no undissolved components.

The present invention is particularly useful for the followingapplications: in home applications, such as furniture, wood floors,chipboards or timber work; outdoor applications, such as fences,construction parts, wooden fronts, window frames and the like.

The present coatings compositions may be applied to the substrates bythe customary methods, for example by brushing, spraying, pouring,dipping or electrophoresis; see also Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 491-500.

Depending on the binder system, the coatings may be cured at roomtemperature or by heating. The coatings may for example be cured at 50to 150° C., and, e.g. in the case of powder coatings or coil coatings,even at higher temperatures.

The coating compositions can comprise an organic solvent or solventmixture in which the binder is soluble. The coating compositions canotherwise be an aqueous solution or dispersion. The vehicle can also bea mixture of organic solvent and water. The coating composition may be ahigh-solids paint or can be solvent-free (e.g. a powder coatingmaterial). Powder coatings are, for example, those described inUllmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages438-444. The powder coating material may also have the form of apowder-slurry (dispersion of the powder preferably in water).

The pigments can be inorganic, organic or metallic pigments. The presentcoatings compositions may contain no pigments and may be used as aclearcoat.

The following examples illustrate the invention without restricting it.

EXAMPLES A) Biocide Compositions

Determination of the Minimum Inhibitory Concentration (MIC):

The effects of the biocidal compositions comprising an imidazoliumpolymer were tested in Minimum Inhibitory Concentration tests againstStaphylococcus aureus and Pseudomonas aeruginosa as exemplary members ofthe harmful microorganisms mentioned above. The MIC measurements wereperformed following a procedure described by J. M. Andrews, J.Antimicrobial Chemotherapy, (2001) 48, Suppl. S1, 5-16 based on thecommendations of the British Society for Antimicrobial Chemotherapy.

For pre-cultivation of the bacteria, Staphylococcus aureus ATCC 29213and Pseudomonas aeruginosa ATCC 27853 were streaked onto IsoSensitestagar plates, respectively, and incubated at 37° C. overnight. Singlecolonies were used to inoculate 50 mL of IsoSensitest broth in 250 mL ofbaffled Erlenmeyer flasks at 190 rpm and 37° C. for 15 hours,respectively. Then, 50 mL of IsoSensitest broth were inoculated with theprecultures to a final optical density of OD=0.1, respectively.

Stock solutions of the biocidal composition comprising an imidazoliumpolymer were prepared at 10 mg/mL and 1 mg/mL in deionized water.Dilution series (log 2, from 4096 μg/mL to 0.25 μg/mL) with deionizedwater were made. Concentrations from 4096 μg/mL to 8 μg/mL were madeusing the 10 mg/mL stock solution; Concentrations from 4 μg/mL to 0.25μg/mL were made using the 1 mg/mL stock solution. 75 μl quantities ofeach dilution were added to 8 wells of a 96 well microtiter-plate,respectively. Then, 75 μl of the bacterial suspension with an opticaldensity of OD=0.1 were added to the wells. Wells charged with 75 μl ofwater and 75 μl of non-inoculated IsoSensitest broth served as sterilecontrol. Wells charged with 75 μl of water and 75 μl of bacterialsuspension served as positive control for unrestricted growth. Themicrotiter-plates were incubated for 24 hours at 37° C. and 750 rpm andthe growth of microorganisms was determined by measuring the opticaldensity. The optical density was measured in a time frame from 1.5 h to24 h. As Minimum Inhibitory Concentration, these concentrations weredetermined, where no growth could be observed after 24 h (OD smallerthan 0.1). As a control, three known antibiotics were chosen (J. M.Andrews, J. Antimicrobial Chemotherapy, (2001), 48, Suppl. S1, 5-16) tooffer a comparison of the biocidal composition comprising an imidazoliumpolymer with known antibiotics.

TABLE 1 Imidazolium polymers and their biological activity: MIC MICStaphylococcus Pseudomonas aureus aeruginosa ATCC 29213 = ATCC 27853 =Repeating unit of the imidazolium DSM 2569 DSM 1117 No. Diamine Acidpolymer [μg/mL] [μg/mL] 1 1,4- Butane- diamine Acetic acid

4 4 2 1,4- Butane- diamine Phosphoric acid

4 2 3 1,4- Butane- diamine Methane sulfonic acid

16 8 4 1,4- Butane- diamine Sulfuric acid

2 2 5 1,4- Butane- diamine Hexanoic acid

8 4 6 1,4- Butane- diamine Octanoic acid

8 8 7 1,4- Butane- diamine Adipic acid

32 16 8 1,4- Butane- diamine Terephthalic acid

4 4 9 1,5- Pentane- diamin Acetic acid

4 8 10 1,6- Hexane- diamin Acetic acid

8 64 11 1,6- Hexane- diamin Methane sulfonic acid

8 16 12 1,6- Hexane- diamin [2-(2-methoxy- ethoxy)- ethoxy]-acetic acid

4 8 13 1,12- Dodecane- diamine Acetic acid

8 32 14 Poly(vinyl- formamid- co- vinyl- amine) ca. 50% hydrolysis gradeAcetic acid — 128 15 1,8- Diamino- 3,6- dioxa- octane Acetic acid

16 16 17 1,8- Diamino- 3,6- dioxa- octane Sulfuric acid

32 16 18 Tris(2- Acetic acid 32 — amino- ethylamine) 0.5 parts +1,6-hexane- diamine 0.5 parts 19 Tris(2- Acetic acid 64 amino-ethylamine) 0.5 parts + 1,6-hexane- diamine 1 part 20 Tris(2- Aceticacid 16 — amino- ethylamine) 0.3 parts + 1,6-hexane- diamine 1 part 21Tris(2- Acetic acid 32 — amino- ethylamine) 0.5 parts + 1,4-butane-diamine 0.5 parts 22 Tris(2- Acetic acid 64 — amino- ethylamine) 0.3parts + 1,4-butane- diamine 1 parts 23 Tris(2- Acetic acid 64 — amino-ethylamine) 0.7 parts 24 Tris(2- Acetic acid 64 — amino- ethylamine) 0.5parts + ethylene diamine 0.5 parts

TABLE 2 Known biocidal polymers and their biological activity MIC MICPseudomonas Staphylococcus aeruginosa aureus ATCC ATCC 27853 =Comparative structure of the prior art 29213 = DSM DSM 1117 No. polymerspolymer 2569 [μg/mL] [μg/mL] C1 Poly(vinylformamid- 256 256co-vinylamine) >90% hydrolysis grade C2 1,3- Dibutyl- imidazoliumacetate

2048 4096

TABLE 3 Known antibiotics and their biological activity as control MICMIC Staphylococcus Pseudomonas aureus aeruginosa ATCC 29213 = ATCC 27853= Control DSM 2569 DSM 1117 No. antibiotics [μg/mL] [μg/mL] Control 1Cephalexine 4 >4096 Control 2 Tetracycline 1 32 Control 3 Nalidixic acid64 1024

B) Cosmetic Compositions

The active materials (AM) are given in percentages.

Examples 1 to 4 (Shampoo Compositions)

In g AM example no. 1 2 3 4 Cocoglucoside [1] 5 5 5 5 Cocoamidopropyl5.4 5.4 5.4 5.4 betaine [2] Sodium lauryl ether (5 OE) carboxylate [3] 33 3 3 Sodium lauryl ether sulfate [4] 4 4 4 4 Imidazolium compoundaccording to 0.4 0.4 0.4 0.4 example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 Polydimethylsiloxane2.6 1 0.5 0.1 (Dimethicone) [5] Preserving agent qs qs qs qs Fragranceqs qs qs qs Citric acid qs qs qs qs pH 6.5 6.5 6.5 6.5 Water qs 100 g100 g 100 g 100 g [1] PLANTACARE ® 818 UP sold by Cognis [2] DEHYTO ® AB30 sold by Cognis [3] AKYPO ® RLM 45 CA sold by KAO [4] TEXAPON ® N 702sold by Cognis [5] DC 200 Fluid 60000 CS sold by Dow Corning

Example 5 (Hair Conditioner with Anionic Associative Polymer)

Imidazolium compound according to example 1, 1 g 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 Methacrylicacid/ethyl acrylate/oxyethylenated 0.1 g AM (25 EO) behenyl methacrylateterpolymer as an aqueous emulsion (20 wt %) [1] Chlorhexidinedigluconate solution 0.2 g Methyl p-hydroxybenzoate 0.3 g Lactic acid qspH 4.0 +− 0.2 Cetylstearyl alcohol [2]g 5 g Water qs 100 g [1] soldunder the trade name Aculyn 28 by Rohm & Haas [2] sold under the tradename Lanette O OR by the company Cognis

The obtained hair conditioner composition was stable and viscous. Whenapplied to wet hair after shampooing, it could be easily applied, had agood spreadability and good wash-out properties. The treated hair wassmooth and shiny.

Example 6 (Antidandruff Shampoo Composition)

Sodium lauryl ether sulphate (2.2 EO) 17 g AM Cocoylbetaine as anaqueous 30% solution 2.5 g AM (DEHYTON AB 30 from Henkel) Terpolymer ofmethacrylamidopropyl- 1 g AM trimethylammonium chloride, acrylic acidand stearyl methacrylate (49 mol %/49 mol %/2 mol %) Sodium cetostearylsulphate 0.75 g Coconut acid monoisopropanolamide 0.6 g Imidazoliumcompound according to example 1, 2, 0.5 g 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 Preserving agents,fragrance qs Water qs 100 g

Example 7 (Cream for Treatment of Acne and Hyperseborrhoea)

Imidazolium compound according to example 1, 2, 1.00% 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 Sorbitanetristearate 1.00% perfume 0.30% crosslinked acrylic acid homopolymer0.40% xanthane gum 0.50% copolymer of ethylene glycoldimethacrylate/lauryl 1.00% methacrylate cyclopenta dimethylsiloxane6.00% glycerine 3.00% mixture of cetyl/stearyl alcohol, ethoxylatedstearyl 4.00% alcohol (6 EO and 32 EO) demineralized water qs 100

Example 8 (Mineral Oil)

oleth-5 5.00 cetyl alcohol (and) behentrimonium 1.00 methosulfate (and)Quaternium-33 2-oleamido-1,3-octadecandiol 0.10 oleth-20 5.00Imidazolium compound according to example 1, 0.50 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24

Example 9 (Foam Conditioner)

[%] Imidazolium compound according to example 1, 2, 3, 4, 5, 6, 7, 8,20.00 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24Cremophor A 25 (Ceteareth 25/BASF) 0.2 Comperlan KD (Coamide DEA/Henkel)0.1 Water 69.7 Propane/butane 10.0 Further additive: perfume,preservative . . .

Preparation: Weigh in and dissolve with stirring. Bottle and addpropellant gas.

Example 10 (Hair Gel)

[%] Phase 1: Imidazolium compound according to example 1, 2, 3, 4, 5, 6,7, 8, 12.00 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24 Water, dist. 37.00 Aminomethylpropanol (38% strength solution) 1.0Further additive: preservative, soluble ethoxylated silicone, perfume .. . Phase 2: Aculyn 28 (1% strength aqueous suspension) 50.00

Preparation:

Phases 1 and 2 are weighed in and homogenized separately. Phase 2 isthen slowly stirred into phase 1. An essentially clear, stable gelforms.

Example 11 (Hair Gel)

[%] Phase 1: Imidazolium compound according to example 1, 2, 3, 4, 5, 6,7, 8, 12.00 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24 Water, dist. 30.00 Further additive: preservative, solubleethoxylated silicone, perfume . . . Phase 2: Natrosol HR 250 (5%strength solution) 50.00 Hydroxyethylcellulose (Hercules)

Preparation:

Phases 1 and 2 are weighed in and homogenized separately. Phase 2 isthen slowly stirred into phase 1. An essentially clear, stable gelforms.

C) Fungicidal Activity

The following polymers F1 to F27 were prepared according to theprocedures described in WO 2010/0725721. C1 is a comparative example.

The α-dicarbonyl compound a) used was glyoxal, the aldehyde b) used wasa formaldehyde source and the diamine c) used is indicated in the table.

Polymers F28 and F29 were prepared as follows:

F28: 1,4-Diaminobutane (1.1 mol) and glyoxal (1.1 mol) were added atroom temperature simultaneously dropwise to benzaldehyde (1.1 moles) inof acetic acid (4.3 mol). The mixture was heated for three hours toreflux. Water was distilled off to give the polymer as a dark oil.

¹H-NMR (D₂O) δ=7.86-7.15 (m, 1H); 4.31-4.18 (m, 0.3H); 3.31-2.99 (m,0.5H); 2.05 (s, 1.6H); 2.01-1.83 (m, 0.8H).

F29: The polymer was prepared in analogy to polymer F28, using howeverdodecanal as aldehyde.

¹H-NMR (D₂O) δ=7.61-7.48 (m, 1H); 4.32-4.15 (m, 2.2H); 3.10-2.96 (m,2.5H); 2.04 (s, 21H); 2.01-1.86 (m, 3.3H); 1.81-1.65 (m, 3.2H);1.47-1.14 (m, 12H).

M_(w) is the weight-average molecular weight as obtained by GPC (gelpermeation chromatography/size exclusion chromatography) using 0.02mol/l formic acid+0.2 mol/l KCl in water as elution agent and pullulanstandard (linear polymaltotriose and maltohexose; from PSS, Germany), orusing hexafluoroisopropanol+0.05% potassium trifluoroacetate in water aselution agent and PMMA standard. PDI is the polydispersity M_(w)/M_(n)(M_(n)=number-average molecular weight).

No. amine repeating units M_(w) PDI F1 1,4-diamino-butane

30000 8 F2 1,4-diamino-butane

F3 1,4-diamino-butane

F4 1,6-diamino-hexane

F5 1,4-diamino-butane

F6 1,6-diamino-hexane

10700 5.4 F7 2,6-diamino-hexanoic acid

10200 4.3 F8 1,6-diamino-hexane

19600 12.3 F9 NH₂—(CH₂)₃—(OCH₂CH₂)O—(CH₂)₃—NH₂

F10 NH₂—[(CH₂)₂O]₂—(CH₂)₂—NH₂

F11 NH₂—[(CH₂)₂O]₂—(CH₂)₂—NH₂

F12 1,4-diamino-butane

10000 7.2 F13 1,4-diamino-butane

13200 6.4 F14 1,6-diamino-hexane

F15 1,4-diamino-butane

38500 2.5 F16 1,12-diamino-dodecane

70000 2.5 F17 1,4-diamino-butane

2310 F18 1,4-diamino-butane

112000 F19 1,4-diamino-butane

40000 F20 1,4-diamino-butane

8770 F21 80% 1,4-diamino-butane + 20% anion: acetate 3000CH₃CH₂C—(OCH₂CH₂—CH(CH₃)NH₂)₃ F22 see F21 anion: acetate 14000 F23Bis(4-amino-cyclohexyl)-methane

12000 F24 1,8-diamino-octane

43000 F25 1,6-diamino-hexane

70000 F26 3-amino-methylbenzyl-amine

20000 F27 isophoron-diamine

49800 F28 1,4-diamino-butane

1200 1.9 F29 1,4-diamino-butane

C1 1,4-diamino-2-hydroxy-propane

C.1) Green House Tests

The spray solutions were prepared in several steps:

The stock solutions were prepared: a mixture of acetone and/ordimethylsulfoxide and the wetting agent/emulsifier Wettol, which isbased on ethoxylated alkylphenoles, in a relation (volume)solvent-emulsifier of 99 to 1 was added to 25 mg of the active compoundto give a total of 5 ml. Water was then added to total volume of 100 ml.This stock solution was diluted with the describedsolvent-emulsifier-water mixture to the given concentration.

C.1.1) Preventative Fungicidal Control of Botrytis cinerea on Leaves ofGreen Pepper

Young seedlings of green pepper were grown in pots to the 4 to 5 leafstage. These plants were sprayed to run-off with an aqueous suspension,containing the concentration of active ingredient or their mixturementioned in the table below. The next day the plants were inoculatedwith an aqueous biomalt solution containing the spore suspension ofBotrytis cinerea. Then the plants were immediately transferred to ahumid chamber. After 5 days at 22 to 24° C. and a relative humidityclose to 100% the extent of fungal attack on the leaves was visuallyassessed as % diseased leaf area.

The untreated control showed 90% disease.

Plants treated with 250 ppm of compounds F1 and F13, respectively, hadat most 40% diseased leaf area. Plants treated with 250 ppm of compoundC1 showed 90% diseased leaf area.

Plants treated with 500 ppm of compounds F1, F5, F8, F11, F18, F20 andF26, respectively, had at most 7% diseased leaf area.

C.1.2) Protective Control of Soy Bean Rust on Soy Beans Caused byPhakopsora pachyrhizi

Leaves of pot-grown soy bean seedlings were sprayed to run-off with anaqueous suspension, containing the concentration of active ingredient ortheir mixture as described below. The plants were allowed to air-dry.The trial plants were cultivated for 1 day in a greenhouse chamber at23-27° C. and a relative humidity between 60 and 80%. Then the plantswere inoculated with spores of Phakopsora pachyrhizi. To ensure thesuccess the artificial inoculation, the plants were transferred to ahumid chamber with a relative humidity of about 95% and 20 to 24° C. for24 h. The trial plants were cultivated for fourteen days in a greenhousechamber at 23-27° C. and a relative humidity between 60 and 80%. Theextent of fungal attack on the leaves was visually assessed as %diseased leaf area.

The untreated control showed 70% diseased leaf area.

Plants treated with 250 ppm of compounds F1 and F15, respectively, hadat most 30% diseased leaf area. Plants treated with 250 ppm of compoundC1 showed 70% diseased leaf area.

Plants treated with 500 ppm of compounds F2, F3, F4, F5, F10, F13, F14,F21, F22, F23, F24 and F25, respectively, had at most 20% diseased leafarea.

C.1.3) Control of Late Blight on Tomatoes Caused by Phytophthorainfestans

Young seedlings of tomato plants were grown in pots. These plants weresprayed to run-off with an aqueous suspension, containing theconcentration of active ingredient or their mixture mentioned in thetable below. The next day, the treated plants were inoculated with anaqueous suspension of sporangia of Phytophthora infestans. Afterinoculation, the trial plants were immediately transferred to a humidchamber. After 6 days at 18 to 20° C. and a relative humidity close to100% the extent of fungal attack on the leaves was visually assessed as% diseased leaf area.

The untreated control showed 90% diseased leaf area.

Plants treated with 500 ppm of compounds F1, F8, F11, F15, F16, F18,F22, F23, F24, F25 and F26, respectively, had at most 20% diseased leafarea.

C.2) Microtests

The active compounds were formulated separately as a stock solutionhaving a concentration of 10000 ppm in dimethyl sulfoxide.

C.2.1) Activity Against the Grey Mold Botrytis cinerea in theMicrotiterplate Test (Botrci)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Botrci cinerea in an aqueousbiomalt or yeast-bactopeptone-sodiumacetate solution was then added. Theplates were placed in a water vapor-saturated chamber at a temperatureof 18° C. Using an absorption photometer, the MTPs were measured at 405nm 7 days after the inoculation.

The measured parameters were compared to the growth of the activecompound-free control variant (100%) and the fungus-free and activecompound-free blank value to determine the relative growth in % of thepathogens in the respective active compounds.

C.2.2) Activity Against the Late Blight Pathogen Phytophthora infestansin the Microtiter Test (Phytin)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Phytophtora infestans containing apea juice-based aqueous nutrient medium or DDC medium was then added.The plates were placed in a water vapor-saturated chamber at atemperature of 18° C. Using an absorption photometer, the MTPs weremeasured at 405 nm 7 days after the inoculation.

The measured parameters were compared to the growth of the activecompound-free control variant (100%) and the fungus-free and activecompound-free blank value to determine the relative growth in % of thepathogens in the respective active compounds.

C.2.3) Activity Against Leaf Blotch on Wheat Caused by Septoria tritici(Septtr)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Septoria tritici in an aqueousbiomalt or yeast-bactopeptone-glycerine solution was then added. Theplates were placed in a water vapor-saturated chamber at a temperatureof 18° C. Using an absorption photometer, the MTPs were measured at 405nm 7 days after the inoculation.

The measured parameters were compared to the growth of the activecompound-free control variant (100%) and the fungus-free and activecompound-free blank value to determine the relative growth in % of thepathogens in the respective active compounds.

Growth (%) Growth (%) Growth (%) Compound at 32 pm at 32 pm at 32 pm no.Botrci Phytin Septtr F1 0 F3 0 F4 0 F5 0 F6 0 1 0 F8 0 F11 0 F12 0 0 0F13 0 F15 0 F16 2C.3) Microtests with Mixtures of Active Compounds

The active compounds were formulated separately as a stock solutionhaving a concentration of 10000 ppm in dimethyl sulfoxide.

C.3.1) Activity Against the Late Blight Pathogen Phytophthora infestansin the Microtiter Test (Phytin)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Phytophtora infestans containing apea juice-based aqueous nutrient medium or DDC medium was then added.The plates were placed in a water vapor-saturated chamber at atemperature of 18° C. Using an absorption photometer, the MTPs weremeasured at 405 nm 7 days after the inoculation.

The measured parameters were compared to the growth of the activecompound-free control variant (100%) and the fungus-free and activecompound-free blank value to determine the relative growth in % of thepathogens in the respective active compounds. These percentages wereconverted into efficacies.

The expected efficacies of active compound mixtures were determinedusing Colby's formula [R. S. Colby, “Calculating synergistic andantagonistic responses of herbicide combinations”, Weeds 15, 20-22(1967)] and compared with the observed efficacies.

Calculated efficacy Active Con- according compound/ centration Observedto Colby Synergism active mixture (ppm) Mixture efficacy (%) (%) F15 1 —46 Pyraclostrobin 0.063 — 24 Epoxiconazole 0.25 — 11 Azole* 4 — 20Fluxapyroxad 0.063 — 12 F15 1 16:1  87 59 28 Pyraclostrobin 0.063 F15 14:1 86 52 34 Epoxiconazole 0.25 F15 1 1:4 91 57 34 Azole* 4 F15 1 16:1 84 53 31 Fluxapyroxad 0.063C.3.2) Activity Against the Grey Mold Botrytis cinerea in theMicrotiterplate Test (Botrci)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Botrci cinerea in an aqueousbiomalt or yeast-bactopeptone-sodiumacetate solution was then added. Theplates were placed in a water vapor-saturated chamber at a temperatureof 18° C. Using an absorption photometer, the MTPs were measured at 405nm 7 days after the inoculation.

Calculated efficacy Active Con- according compound/ centration Observedto Colby Synergism active mixture (ppm) Mixture efficacy (%) (%) F15 1 —18 Pyraclostrobin 0.016 — 0 Epoxiconazole 0.063 — 34 Azole* 1 — 15Fluxapyroxad 0.016 — 13 F15 1 63:1 69 18 51 Pyraclostrobin 0.016 F15 116:1 99 45 54 Epoxiconazole 0.063 F15 1  1:1 100 30 70 Azole* 1 F15 163:1 98 28 70 Fluxapyroxad 0.016C.3.3) Activity Against Rice Blast Pyricularia oryzae in theMicrotiterplate Test (Pyrior)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Pyricularia oryzae in an aqueousbiomalt or yeast-bactopeptone-glycerine solution was then added. Theplates were placed in a water vapor-saturated chamber at a temperatureof 18° C. Using an absorption photometer, the MTPs were measured at 405nm 7 days after the inoculation.

Calculated efficacy Active Con- according compound/ centration Observedto Colby Synergism active mixture (ppm) Mixture efficacy (%) (%) F15 4 —8 1 — 0 F19 4 — 14 1 — 5 Azole* 16 — 65 Epoxiconazole 0.25 — 5 F15 1 1:16 96 65 31 Azole* 16 F15 4 16:1 66 12 54 Epoxiconazole 0.25 F19 1 1:16 86 67 19 Azole* 16 F19 4 16:1 36 18 18 Epoxiconazole 0.25C.3.4) Activity Against Leaf Blotch on Wheat Caused by Septoria tritici(Septtr)

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Septoria tritici in an aqueousbiomalt or yeast-bactopeptone-glycerine solution was then added. Theplates were placed in a water vapor-saturated chamber at a temperatureof 18° C. Using an absorption photometer, the MTPs were measured at 405nm 7 days after the inoculation.

Calculated efficacy Active Con- according compound/ centration Observedto Colby Synergism active mixture (ppm) Mixture efficacy (%) (%) F190.016 — 0 F24 0.063 — 1 Pyraclostrobin 0.001 — 38 Azole* 4 — 40 0.25 — 4F19 0.016 16:1  63 38 25 Pyraclostrobin 0.001 F24 0.063 1:4 33 4 29Azole* 0.25 Azole* =2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazole-3-thiol

1-43. (canceled)
 44. A biocide composition comprising at least onepolymeric, ionic compound comprising imidazolium groups (imidazoliumcompound), obtainable by reacting a) at least one α-dicarbonyl compound,b) at least one aldehyde, c) at least one amino compound having at leasttwo primary amino groups, d) optionally an amino compound having onlyone primary amino group and e) at least one protic acid, and optionallysubjecting the reaction product to an anion exchange, where in thecomponents a) and b) the aldehyde carbonyl groups may also be present ashemiacetal or acetal and the ketone carbonyl groups may also be presentas hemiketal or ketal; where the main chain of the at least one compoundcomprising imidazolium groups does not contain 1,4-bound phenylenerings; where the amino compound having at least two primary amino groupsis not 1,3-diamino-2-hydroxy-propane or1,3-diamino-2-hydroxy-2-methyl-propane; and where the polymer comprisesat least 8 imidazolium rings; and at least one carrier and/or at leastone auxiliary agent.